Journal of Geochemical Exploration 188 (2018) 95–100

Contents lists available at ScienceDirect

Journal of Geochemical Exploration

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

Adsorption isotherms, kinetics and thermodynamics of nitrate and T

phosphate in binary systems on a novel adsorbent derived from corn stalks
⁎
Chunhui Fana,c, , Yingchao Zhangb
a
School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China
b
School of Environment, Tsinghua University, Beijing 100084, China
c
Department of Soil and Crop Sciences, Colorado State University, Fort Collins 80523, USA

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

Keywords: Novel adsorbents from raw corn stalks (RCS) were synthesised after cellulose isolation followed by modification
Cellulose with epichlorohydrin, N,N-dimethylformamide, pyridine and diethylamine. The MCCS (modified cellulose from
Corn stalks corn stalks) products were characterised by thermogravimetric analysis, elemental analysis, scanning electron
Nitrate microscopy–energy dispersive spectrometry (SEM-EDS) and Fourier transform infrared spectroscopy (FT-IR);
Phosphate
moreover, the adsorption characteristics of nitrate and phosphate on MCCS were investigated in binary systems
Adsorption
using batch adsorption procedures. The mass loss of RCS and MCCS may be divided into three stages and the
modification reaction increased the stability of samples. The surface of MCCS was rougher than that of RCS and
amine groups were successfully loaded onto MCCS, as shown by elemental analysis results and FT-IR spectra.
The pseudo-second order kinetics equation and Langmuir isotherm could well describe the adsorption process,
and the maximum adsorption capacities (298 K) of nitrate and phosphate on MCCS as calculated from the
Langmuir isotherm were 13.6054 and 22.8833 mg/g, respectively. The obtained thermodynamic parameters
indicated the spontaneous and exothermic nature of adsorption.

1. Introduction yearly. Stalk is an important natural biomass resource; statistically,

With the developments in the economy and society, various human
activities, such as agricultural, industrial and household, have increased
wastewater with high contents of nitrate and phosphate (Rodrigues and
Pinto da Silva, 2010; Bhatnagar and Sillanpaa, 2011). At present, ni-
trate and phosphate in wastewater are the focus of numerous in-
vestigations of contaminants, because their increasing concentration
may cause eutrophication in aquatic environments. Treatment methods
for wastewater contaminated with nitrates and phosphates include
membrane filtration (Zularisam et al., 2006), ion exchange (Patrick
et al., 2012) and biofiltration (Martin et al., 2009). Adsorption is found
to be one of the most appropriate technologies owing to its low cost,
ease of handling and acceptable efficiency (Gil et al., 2011; Ngah et al.,
2011).
Adsorption refers to the interaction of an adsorbate and an ad-
sorbent between the gas, solid and liquid interfaces and involves the
adsorption mechanisms of Van der Waals force, complexation, hy-
drogen bond, ion exchange and co-precipitation (Fletcher et al., 2006;
Ahmet et al., 2007). Currently, a series of novel adsorbents, including
adsorbents obtained from agricultural wastes of stalk, are synthesised
approximately 0.7 billion tons of crop stalks are produced annually in
China, with a reutilisation rate lower than 50% (Norse, 2005). Studies
have showed that various kinds of stalks (corn stalk, rice stalk, wheat
stalk and sorghum stalk) have been used to remove contaminants from
aqueous solutions with acceptable treatment efficiencies (Robinson
et al., 2002; Haque et al., 2007; Cao et al., 2011). The products of stalks
after chemical modification may improve the composition structure or
introduce functional groups onto the stalk surface, further benefitting
the enhancement of adsorption capacity (Husseien et al., 2009).
Corn stalks (CS) are the most abundant of agricultural stalks. CS are
rich in cellulose, the structure of which contains a large amount of
hydroxyl groups (functional groups for pollutants removal) (Lu and
Hsieh, 2012). Previous studies have shown the adsorption behaviour of
nitrates, phosphates or heavy metals on CS in a single system (Chen
et al., 2011a); in fact, the adsorption capacity on anions can be mark-
edly enhanced based on adsorbent modification. This investigation
aims to develop a novel adsorbent from raw CS (RCS), which have been
scarcely studied. In this paper, modified cellulose from CS (MCCS) was
prepared from RCS after reacting with epichlorohydrin and triethyla-
mine in the presence of N,N-dimethylformamide (DMF) using

⁎
Corresponding author at: School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China.
E-mail addresses: fanchunhui@sust.edu.cn (C. Fan), zyc036@mail.tsinghua.edu.cn (Y. Zhang).

https://doi.org/10.1016/j.gexplo.2018.01.020
Received 6 April 2017; Received in revised form 22 September 2017; Accepted 23 January 2018
Available online 04 February 2018
0375-6742/ © 2018 Elsevier B.V. All rights reserved.
C. Fan, Y. Zhang Journal of Geochemical Exploration 188 (2018) 95–100

diethylenetriamine (DETA) as a modifying agent. The reactions in the
preparation of the anion adsorbent (MCCS) consisted of polymerisation,
chelating and crosslinking, which may increase adsorption efficiency by
introducing special functional groups to RCS (Xu et al., 2016). MCCS,
together with RCS, were characterised by thermogravimetric analysis
(TGA), elemental analysis, scanning electron microscopy with energy
dispersive spectrometry (SEM-EDS) and Fourier transform infrared
spectroscopy (FT-IR); moreover, the adsorption isotherms, adsorption
kinetics and thermodynamic studies were investigated in binary sys-
tems. The achievements were of considerable importance for revealing
the mechanism of nitrate and phosphate adsorption on MCCS in the
future.
2. Materials and methods
2.1. Materials and chemicals
RCS samples were obtained from Xi'an, Shaanxi Province in north-
western China. After being washed with purified water thrice, RCS was
smashed into fragments with the average length of 5 mm and dried at
60 °C to constant weight for future use. All reagents used were of
analytical grade and provided by Kermel Chemical Reagent Co., Ltd.
2.2. Experimental methods
2.2.1. Isolation of cellulose
The isolation process of cellulose from RCS was as follows (Liu et al.,
2007): first, 10 g of RCS was mixed with 150 mL of 5% NaOH solution
at 55 °C for 1.5 h, filtrated and washed with purified water thrice and
dried at 60 °C for 6 h. Secondly, the dried residues were treated with
35 mL of NaClO2 solution (9.5 g/L) and 100 mL of acetic acid (10%) at
75 °C for 1 h. Third, the filtered product was washed with acetone and
purified water successively and the samples were dried at 60 °C for 6 h.
Cellulose from RCS was obtained successfully.
2.2.2. Modification of cellulose
Cellulose modification was conducted in a 500 mL three-neck round
bottom flask that contained 2 g of cellulose samples, 40 mL of epi-
chlorohydrin and 120 mL of DMF and stirred continuously at 100 °C for
1 h. Then, 16 mL of pyridine was added into the flask and stirred at
100 °C for 1 h; afterwards, 30 mL of diethylamine was mixed into the
flask and the contents were stirred at 100 °C for 2 h. After the reaction,
the filtrated samples were washed with NaOH solution (0.1 mol/L), HCl
(0.1 mol/L), ethanol (50%) and purified water successively and dried at
60 °C for 12 h. The obtained product, MCCS, was used as the adsorbent
in the following research.
The synthesis reaction of MCCS can be found in our previous work
(Fan et al., 2015). The preparation of MCCS involved the chain reac-
tions between the cellulose/hemicellulose chain and side chains of
different grafting chemical reagents. In general, glycosyl was first ty-
pically reacted with a crosslinking agent (epichlorohydrin) to produce
hydroxy glycosyl ether; then, the organic medium (DMF) was used to
enhance the susceptibility of the epoxide ring in epichlorohydrin. Thus,
hydroxy glycosyl ether can react effectively with diethylamine in the
excessive epichlorohydrin environment.
were not covered with the golden film to better preserve their surface
nature, and a conductive adhesive was used to increase their electro-
conductivity. The FT-IR spectra were obtained in the range of
4000–400 cm−1 on a spectrometer (Vector22, Bruker, Germany) by the
KBr pellet method at room temperature.
2.4. Adsorption experiments
Standard nitrate and phosphate stock solution was prepared by
dissolving an appropriate amount of sodium nitrate (NaNO3) and po-
tassium dihydrogen phosphate (KH2PO4) into water. The nitrate and
phosphate solution was obtained by stepwise dilution of the stock so-
lutions with purified water. The batch adsorption procedures were
conducted to reveal the adsorption isotherms by adding 0.1 g of MCCS
into a series of flasks with the nitrate and phosphate solution
(0.5–100 mg/L) for 6 h at initial pH values (6.80 ± 0.10) and different
temperature (288, 298 and 308 K). The adsorption kinetics were in-
vestigated by mixing 0.1 g of MCCS with 50 mL of nitrate solution
(100 mg/L) and 50 mL of phosphate solution (100 mg/L) in each flask
at initial pH values (6.80 ± 0.10) and temperature of 288, 298 and
308 K in an orbital shaker at 120 rpm. The investigation was conducted
in triplicate. At certain time intervals, MCCS was filtered off and the
concentrations of nitrate (210 nm) and phosphate (700 nm) were
measured using a UV–visible spectrophotometer (UV2600, Unico,
USA).
3. Results and discussion
3.1. Characterization of RCS and MCCS
3.1.1. TGA
TGA is useful in determining the thermal stability and decomposi-
tion behaviour of experimental samples (Maria et al., 2011). The TGA
curves of RCS and MCCS are shown in Fig. 1. In general, the mass loss of
TG curves could be divided into three stages. The first stages for RCS
(35 °C to 200 °C) and MCCS (35 °C to 250 °C) may be due to the eva-
poration of water molecules, corresponding to mass losses of 9.04% and
13.20%, respectively. The second stage, which occurred from 200 °C to
450 °C for RCS and 250 °C to 450 °C for MCCS, was significant for mass
loss during the pyrolysis process and 64.82% (RCS) and 55.86%
(MCCS) of total mass losses were observed, thereby revealing that the
decomposition of cellulose, hemi-cellulose or lignin mainly occurred in
these temperature ranges. Mass loss in the third stage (450 °C to 600 °C)
was minimal, indicating the presence of stable oxides at high tem-
perature. The significant decomposition temperatures of RCS and MCCS
started from 200 °C and 250 °C, respectively, confirming that the
modification reaction may increase the stability of the sample compo-
sition.

2.3. Characterization of RCS and MCCS

To investigate the pyrolysis behaviour of RCS and MCCS, the TGA

curves were recorded using a thermogravimetric analyser (STA409PC,
Netzsch, Germany) at the heating rate of 10 °C/min from 30 °C to 600 °C
in a nitrogen atmosphere. An elemental analyser (Vario EL III,
Elemeraor, Germany) was used for the determination of N, C and H. The
surface morphology and elemental composition of RCS and MCCS were
revealed using SEM (S4800, Hitachi, Japan) equipped with an energy
Fig. 1. TGA curves of RCS and MCCS samples.
dispersive X-ray spectroscope (EX350, Horiba, Japan). The samples

96
C. Fan, Y. Zhang Journal of Geochemical Exploration 188 (2018) 95–100

Table 1 Table 2
Elemental contents of RCS and MCCS samples. EDS analysis of RCS and MCCS samples.

N/(%) C/(%) H/(%) RCS MCCS

RCS 1.32 40.46 6.27 C N O Cl C N O Cl

MCCS 6.09 53.84 6.95
Wt/(%) 39.14 5.89 45.35 2.84 53.85 8.28 26.18 11.69
At/(%) 48.16 6.21 41.88 1.18 63.68 8.40 23.24 4.68
3.1.2. Elemental analysis
The elemental content variations of RCS and MCCS are shown in
Table 1. In the RCS sample, the contents of nitrogen, carbon and hy-
drogen were 1.32%, 40.46% and 6.27%, respectively. After the mod-
ification reaction, the contents of three elements in MCCS increased
significantly. In particular, the nitrogen content reached to 6.09%,
confirming that related functional groups (amine groups) were suc-
cessfully loaded onto the cellulose molecules in the modification pro-
cess.

3.1.3. SEM-EDS
The surface characteristics of RCS and MCCS are revealed in Fig. 2.
RCS presented a smoother surface than MCCS, and burr-like protrusions
and cracks appeared on the irregular surface of MCCS, thereby in-
dicating that the modification reaction may be effective for the struc-
ture damage and surface variations on RCS. The overall chemical
Fig. 3. FT-IR spectra of RCS and MCCS samples.
compositions of RCS and MCCS were further validated in Table 2. In
general, carbon and oxygen are the most important elements in RCS
and MCCS, accounting for 84.49% and 80.03% of total weight (wt%), 1338 cm−1 is assigned to the CeN stretching vibration of the amine
respectively. The increased content of nitrogen was detected in the groups (Wahab et al., 2010). The FT-IR spectra indicated that the
composition of MCCS, corresponding with the results above. modification reaction resulted in the intensity variation and peak shift,
and the functional groups (amine groups) were successfully loaded onto
MCCS samples.
3.1.4. FT-IR
The functional groups of RCS and MCCS are shown in the FT-IR
spectra (Fig. 3). The two spectra presented similar characteristics and
3.2. Adsorption isotherms
adsorption peaks indicated the complex nature of the sample compo-
sitions. The strong and broad band around 3400 cm−1 of RCS and
The adsorption equilibria of nitrate and phosphate on MCCS at
MCCS could be assigned to the OeH groups, carboxylic groups or amide
different temperatures are shown in Fig. 4. As seen in the figure, the
NeH stretching, corresponding to the vibration of functional groups in
adsorption capacity of qe increased correspondingly with increasing
cellulose or hemi-cellulose (Gnanasambandam and Protor, 2000). The
concentrations of nitrate and phosphate because the mass transfer
adsorption peak at approximately 2925 cm−1 was reported to be the
driving force increased as the initial concentration increased, thereby
symmetric or asymmetric stretching vibrations of CeH bonds in CH2
increasing adsorption capacity (Nasuha et al., 2010). The adsorption
and CH3 groups. The peak located at 1720 cm−1 was attributed to the
capacity of nitrate and phosphate on MCCS were 12.42 and 20.13 mg/g
stretching vibration of C]O in carboxylic acids and the band intensity
at 100 mg/L and 288 K, respectively. The decreased values of qe at the
reduced in MCCS. The intense band in the region of 1600 cm−1 con-
increased temperature revealed that the adsorption process may be
firmed the aromatic structures related to C]C vibrations. The de-
exothermic to a certain extent.
creased adsorption peak in MCSS at 1250 cm−1 was caused by the
To further explain the solid–liquid adsorption characteristics in
stretching vibration of C]O in phenols (Cesar and Marco, 2004). The
binary systems, Langmuir and Freundlich isotherms were used to es-
CeH and CeO bands of cellulose in MCCS could be observed from 1080
tablish a correlation of the equilibrium curves. The Langmuir isotherm
to 1040 cm−1, and the decreased intensity might be caused by the
assumes monolayer coverage on the adsorbent, and the linearised form
damaged cellulose structure. In the FT-IR spectra of MCCS in Fig. 3, the
is (Langmuir, 1916):
new peaks appear at 1634 and 1029 cm−1 and reveal the presence of
the amine groups (Chen et al., 2011b), and the band at approximately

Fig. 2. SEM micrographs of RCS and MCCS samples.

97
C. Fan, Y. Zhang Journal of Geochemical Exploration 188 (2018) 95–100

Fig. 4. Adsorption equilibrium of nitrate and phosphate on

MCCS at different temperatures.

ce 1 c phosphate were favourably adsorbed on MCCS for the value of n in the

= + e
qe ka qm qm
where qe (mg/g) is the amount adsorbed at equilibrium concentration
ce (mg/L), qm (mg/g) is the Langmuir constant representing maximum
monolayer adsorption capacity and ka (L/mg) is the Langmuir constant
related to the free energy of adsorption.
The Freundlich isotherm assumes heterogeneous surface and ex-
ponential adsorption, and the linearised form is (Freundlich, 1906):
(1) range of 0–1. Moreover, the adsorption capacities of nitrate and phos-
phate on MCCS were acceptable compared with those of other ad-
sorbents (Hamoudi and Belkacemi, 2013; Jiang et al., 2013; Olgun
et al., 2013), and MCCS could be potentially used for water purification
in the future.
3.3. Adsorption kinetics

log qe = log kf + n log ce
where kf (mg/g) is the Freundlich constant related to adsorption ca-
pacity, n is the energy or intensity of adsorption and ce (mg/L) is the
equilibrium concentration.
Constant values and regression coefficients of adsorption isotherms
are listed in Table 3. In general, the Langmuir isotherms yield higher
correlation than Freundlich isotherms for nitrate removal, with coeffi-
cients (R2) of 0.9945–0.9951 and 0.9652–0.9751, respectively; simi-
larly, the Langmuir isotherm (R2 from 0.9915–0.9974) better fit phos-
phate adsorption than Freundlich isotherm (R2 from 0.9484–0.9573)
and the maximum adsorption capacity of nitrate calculated from
Langmuir equation is lower than that of phosphate. As illustrated by the
Donnan theory (Ganguly and Krishnamurti, 1928), the anion charge
may be the key factor responsible for the experimental results in the
adsorption reaction, possibly leading to the preferable adsorption of
phosphate on MCCS over nitrate. The constant values of kf decreased
gradually with increasing temperature. Moreover, the constant value of
n in Freundlich equation was responsible for the type of isotherm
(Andreas, 2004). The value of n in Table 3 indicates that nitrate and
(2) Effects of contact time on the adsorption capacity of nitrate and
phosphate at different temperatures are shown in Fig. 5. The adsorption
process was rapid in the first stage (0–30 min) and followed by a slow
stage (30–120 min) caused by instantaneous monolayer adsorption and
rearrangement of adsorption sites on the surface of MCCS (Yoon et al.,
2009). The adsorption equilibrium times of nitrate and phosphate were
approximately 60 and 75 min, respectively. In the adsorption process of
nitrate and phosphate on MCCS, the adsorption capacity decreased
significantly at higher temperature from 288 to 308 K, indicating the
positive contribution of low temperature for the adsorption process.
Pseudo-first-order and pseudo-second-order equations were used to
further reveal the rate constants and equilibrium adsorption capacities
of nitrate and phosphate on MCCS. The prevailing pseudo-first-order
equation can be described as (Gupta and Bhattacharyya, 2011):
k1
log(qe − qt ) = log qe − t
2.303 (3)
where qe and qt (mg/g) are the amounts of nitrate and phosphate ad-
sorbed at equilibrium time and time t (min), respectively, and k1
(min−1) is the equilibrium rate constant.

Table 3
Isotherm parameters for the adsorption of nitrate and phosphate on MCCS.

T/(K) 288 298 308

Langmuir equation, nitrate

Equation Y = 0.0587x + 0.6028 Y = 0.0735x + 0.6519 Y = 0.092x + 0.6838
ka/(L/mg) 0.0974 0.1127 0.1345
qm/(mg/g) 17.0358 13.6054 10.8696
R2 0.9946 0.9945 0.9951

Freundlich equation, nitrate

Equation Y = 0.608x + 0.1821 Y = 0.5657x + 0.1544 Y = 0.5503x + 0.1009
kf/(mg/g) 1.5209 1.4269 1.2615
n 0.6080 0.5657 0.5503
R2 0.9711 0.9751 0.9652

Langmuir equation, phosphate

Equation Y = 0.0353x + 0.4282 Y = 0.0437x + 0.4193 Y = 0.0461x + 0.5333
ka/(L/mg) 0.0824 0.1042 0.0864
qm/(mg/g) 28.3286 22.8833 21.6920
R2 0.9915 0.9935 0.9974

Freundlich equation, phosphate

Equation Y = 0.7054x + 0.2847 Y = 0.6732x + 0.2652 Y = 0.6931x + 0.1827
kf/(mg/g) 1.9262 1.8416 1.5230
n 0.7054 0.6732 0.6931
R2 0.9573 0.9484 0.9531

98
C. Fan, Y. Zhang Journal of Geochemical Exploration 188 (2018) 95–100

Fig. 5. Adsorption kinetics of nitrate and phosphate on MCCS at

different temperatures.

Table 4
Kinetic parameters for the adsorption of nitrate and phosphate on MCCS.

T/(K) 288 298 308

Pseudo-first order equation, nitrate

Equation Y = −0.0141x + 1.0062 Y = −0.0149x + 0.9443 Y = −0.0151x + 0.8383
k1/(min−1) 0.0325 0.0343 0.0348
qe/(mg/g) 10.1438 8.7963 6.8913
R2 0.9621 0.9573 0.9131

Pseudo-second order equation, nitrate

Equation Y = 0.0625x + 0.5749 Y = 0.0705x + 0.6338 Y = 0.0799x + 0.6132
k2/[g/(mg·min)] 0.0068 0.0078 0.0104
qe/(mg/g) 16.0000 14.1844 12.5156
R2 0.9994 0.9995 0.9994

Pseudo-first order equation, phosphate

Equation Y = −0.0143x + 1.3257 Y = −0.0142x + 1.2098 Y = −0.0161x + 1.154
k1/(min−1) 0.0329 0.0327 0.0371
qe/(mg/g) 21.1691 16.2106 14.2562
R2 0.9785 0.9628 0.9585
Pseudo-second order equation, phosphate
Equation Y = 0.0338x + 0.4758 Y = 0.041x + 0.472 Y = 0.0446x + 0.4714
k2/[g/(mg·min)] 0.0024 0.0036 0.0042
qe/(mg/g) 29.5858 24.3902 22.4215
R2 0.9967 0.9992 0.9988

The integral form of pseudo-second order equation can be written as ΔG 0 = −RT ln K c (5)
(Gupta and Bhattacharyya, 2011):
where R (8.314 J/mol/K) is the ideal gas constant, T (K) is the Kelvin
t 1 t temperature and Kc is the adsorption equilibrium constant, defined
= +
qt k2 qe2 qe (4) according to Aksu as (Aksu, 2002):
ca
where k2 [g/(mg·min)] is the equilibrium rate constant. Kc =
ce (6)
Adsorption kinetics constants and correlation coefficients of nitrate
and phosphate on MCCS are shown in Table 4. Both pseudo-first-order where ca and ce are the equilibrium concentration values in the solid
and pseudo-second-order equations could predict the adsorption pro- phase (mg/L) and in solution (mg/L), respectively.
cess under the experimental conditions. The pseudo-second-order Values of the standard changes of enthalpy (ΔH0) and entropy (ΔS0)
equation described better the adsorption of nitrate and phosphate on are calculated by the equation:
MCCS, considering the calculated values of qe and the obtained coef-
ΔG 0 = ΔH 0 − T ΔS 0 (7)
ficients values of R2. Depending on the pseudo-second-order equation,
the values of qe were markedly close to the experimental qe values of Results of thermodynamic constants at different temperatures are
nitrate and phosphate adsorption at different temperatures. The R2 given in Table 5. The negative values of ΔG0 revealed that adsorption
values of the pseudo-second-order equation (0.9967–0.9995) were su- was spontaneous under experimental conditions. The values of ΔG0
perior to those of the pseudo-first-order equation (0.9131–0.9785). The increased at increased temperature, indicating that the adsorption
results showed that the adsorption of nitrate and phosphate on MCCS process is highly efficient and favourable under low temperature. The
belonged to the second-order reaction and that chemical behaviour was
involved in the adsorption process (Wu et al., 2009). Table 5
Thermodynamic constants for the adsorption of nitrate and phosphate on MCCS.

3.4. Thermodynamic parameters Adsorbate Nitrate Phosphate

T/K 288 298 308 288 298 308

Thermodynamic parameters, including the Gibbs free energy ΔG0/(kJ/ −0.8799 −0.8075 −0.3902 −1.5164 −1.4354 −0.9042
change (ΔG0), enthalpy change (ΔH0) and entropy change (ΔS0), were mol)
determined to evaluate the spontaneous nature and thermodynamic ΔH0/(kJ/ −7.9891 −10.4070
mol)
behaviour of nitrate and phosphate adsorption on MCCS. The standard
ΔS0/(kJ/ −0.0245 −0.0306
change of the Gibbs free energy was obtained by the formula mol/K)
(Kongkachuichay et al., 2002):

99
C. Fan, Y. Zhang
ΔH0 values for nitrate and phosphate adsorption on MCCS were
−7.9891 and −10.4070 kJ/mol, respectively, and the negative values
suggested the exothermic nature of the reaction (Ayhan et al., 2006).
The negative values of entropy change (ΔS0) reflected the affinity va-
lues of nitrate and phosphate on MCCS, thereby indicating certain
structure variations in MCCS and decreasing the interface randomness
between MCCS and aqueous solution (Hulya et al., 2004).
4. Conclusion
The novel MCCS adsorbent was prepared and characterised, and the
adsorption behaviours of nitrate and phosphate on MCCS in binary
systems were investigated. The surface of MCCS was rougher than that
of RCS and the intensity variation of related functional groups appeared
in the FT-IR spectra. The adsorption process could be described by the
Langmuir isotherm and pseudo-second order equation and the max-
imum adsorption capacity, as calculated from the Langmuir equation at
298 K of nitrate and phosphate on MCCS, were 13.6054 and
22.8833 mg/g, respectively. The adsorption of nitrate and phosphate on
MCCS were spontaneous and exothermic. Therefore, MCCS is appro-
priate for nitrate and phosphate removal from aqueous solutions in
binary systems.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (No. 21407103), the Postdoctoral Science
Foundation of China (No. 2012M511968) and the Western Project of
State Scholarship Foundation by the China Scholarship Council (No.
201508615006).
References
Ahmet, S., Mustafa, T., Demirhan, C., Mustafa, S., 2007. Adsorption characteristics of Cu
(II) and Pb(II) onto expanded perlite from aqueous solution. J. Hazard. Mater. 148,
387–394.
Aksu, Z., 2002. Determination of the equilibrium, kinetic and thermodynamic parameters
of the batch biosorption of nickel(II) ions onto Chlorella vulgaris. Process Biochem. 38,
89–99.
Andreas, S.M., 2004. Experimental determination of single solute and competitive ad-
sorption isotherms. J. Chromatogr. A 1037, 255–272.
Ayhan, D., Ahmet, S., Omer, I., 2006. Adsorption thermodynamics of stearic acid onto
bentonite. J. Hazard. Mater. 135, 226–231.
Bhatnagar, A., Sillanpaa, M., 2011. A review of emerging adsorbents for nitrate removal
from water. Chem. Eng. J. 168, 493–504.
Cao, W., Dang, Z., Zhou, X.Q., Yi, X.Y., Wu, P.X., Zhu, N.W., Lu, G.N., 2011. Removal of
sulphate from aqueous solution using modified rice straw: preparation, character-
ization and adsorption performance. Carbohydr. Polym. 85, 571–577.
Cesar, R.T.T., Marco, A.Z.A., 2004. Biosorption of heavy metals using rice milling by-
products. Characterisation and application for removal of metals from aqueous ef-
fluents. Chemosphere 54, 987–995.
Chen, S.H., Yue, Q.Y., Gao, B.Y., Li, Q., Xu, X., 2011a. Removal of Cr(VI) from aqueous
solution using modified corn stalks: characteristic, equilibrium, kinetic and thermo-
dynamic study. Chem. Eng. J. 168, 909–917.
Chen, S.H., Yue, Q.Y., Gao, B.Y., Li, Q., Xu, X., 2011b. Preparation and characteristics of
anion exchanger from corn stalks. Desalination 274, 113–119.
Fan, C.H., Gao, Y.L., Chang, M., 2015. Study on the mechanism to ease the leaching effect
of nutrient in the multi-contaminated loess washing process with the addition of
anion adsorbent (I). J. Shaanxi Univ. Sci. Technol. 33 (3), 16–21 (in Chinese with
English Abstract).
Fletcher, A.J., Yuzak, Y., Thomas, K.M., 2006. Adsorption and desorption kinetics for
100
Journal of Geochemical Exploration 188 (2018) 95–100
hydrophilic and hydrophobic vapors on activated carbon. Carbon 44, 989–1004.
Freundlich, H.M.F., 1906. Uber die adsorption in lasungen. J. Phys. Chem. A 57, 385–470.
Ganguly, P.B., Krishnamurti, S., 1928. An application of the Donnan theory to the ad-
sorption of ions by colloidal silicic acid. Trans. Faraday Soc. 24, 401–405.
Gil, A., Assis, F.C.C., Albeniz, S., Korili, S.A., 2011. Removal of dyes from wastewaters by
adsorption on pillared clays. Chem. Eng. J. 168, 1032–1040.
Gnanasambandam, R., Protor, A., 2000. Determination of pectin degree of esterification
by diffuse reflectance Fourier transform infrared spectroscopy. Food Chem. 68,
327–332.
Gupta, S.S., Bhattacharyya, K.G., 2011. Kinetics of adsorption of metal ions on inorganic
materials: a review. Adv. Colloid Interf. Sci. 162, 39–58.
Hamoudi, S., Belkacemi, K., 2013. Adsorption of nitrate and phosphate ions from aqueous
solutions using organically-functionalized silica materials: kinetic modeling. Fuel
110, 107–113.
Haque, M.N., Morrison, G.M., Perrusquia, G., Gutierrez, M., Aguilera, A.F., Cano-
Aguilera, I., Gardea-Torresdey, J.L., 2007. Characteristics of arsenic adsorption to
sorghum biomass. J. Hazard. Mater. 145, 30–35.
Hulya, G.F., Jens, C.T., David, M., 2004. Adsorption of arsenic from water using activated
neutralized red mud. Environ. Sci. Technol. 38, 2428–2434.
Husseien, M., Amer, A.A., El-Maghraby, A., Hamedallah, N., 2009. A comprehensive
characterization of corn stalk and study of carbonized corn stalk in dye and gas oil
sorption. J. Anal. Appl. Pyrolysis 86, 360–363.
Jiang, H.L., Chen, P.H., Luo, S.L., Tu, X.M., Cao, Q., Shu, M., 2013. Synthesis of novel
nanocomposite Fe3O4/ZrO2/chitosan and its application for removal of nitrate and
phosphate. Appl. Surf. Sci. 284, 942–949.
Kongkachuichay, P., Shitangkoon, A., Chinwongamorn, N., 2002. Thermodynamics of
adsorption of laccaic acid on silk. Dyes Pigments 53, 179–185.
Langmuir, I., 1916. The constitution and fundamental properties of solids and liquids. J.
Am. Chem. Soc. 38, 2221–2295.
Liu, C.F., Sun, R.C., Zhang, A.P., Ren, J.L., Wang, X.A., Qin, M.H., Chao, Z.N., Luo, W.,
2007. Homogeneous modification of sugarcane bagasse cellulose with succinic an-
hydride using a ionic liquid as reaction medium. Carbohydr. Res. 342, 919–926.
Lu, P., Hsieh, Y.L., 2012. Preparation and characterization of cellulose nanocrystals from
rice straw. Carbohydr. Polym. 87, 564–573.
Maria, A.C., Manoli, Z., Milagros, C., Agurtzane, M., 2011. Thermal and thermo-oxidative
degradation of poly (hydroxy ether of bisphenol-A) studied by TGA/FTIR and TGA/
MS. J. Anal. Appl. Pyrolysis 92, 407–416.
Martin, A.J., Kim, D.J., Ren, J.H., Thomas, E.A., 2009. Compost product optimization for
surface water nitrate treatment in biofiltration applications. Bioresour. Technol. 100,
3991–3996.
Nasuha, N., Hameed, B.H., Mohd, D.A.T., 2010. Rejected tea as a potential low-cost ad-
sorbent for the removal of methylene blue. J. Hazard. Mater. 175, 126–132.
Ngah, W.S.W., Teong, L.C., Hanafiah, M.A.K.M., 2011. Adsorption of dyes and heavy
metal ions by chitosan composites: a review. Carbohydr. Polym. 83, 1446–1456.
Norse, D., 2005. Non-point pollution from crop production: global, regional and national
issues. Pedosphere 15, 499–508.
Olgun, A., Atar, N., Wang, S.B., 2013. Batch and column studies of phosphate and nitrate
adsorption on waste solids containing boron impurity. Chem. Eng. J. 222, 108–119.
Patrick, S.B., Thomas, L.T.L., Roberta, C.H.M., Hofman, C., Voogt de, P., Steven, T.J.D.,
2012. Removal of charged micropollutants from water by ion-exchange polymers-
effects of competing electrolytes. Water Res. 46, 5009–5018.
Robinson, T., Chandran, B., Nigam, P., 2002. Effect of pretreatments of three waste re-
sidues, wheat straw, corncobs and barley husks on dye adsorption. Bioresour.
Technol. 85, 119–124.
Rodrigues, L.A., Pinto da Silva, M.L.C., 2010. An investigation of phosphate adsorption
from aqueous solution onto hydrous niobium oxide prepared by co-precipitation
method. Colloids Surf. A Physicochem. Eng. Asp. 334, 191–196.
Wahab, M.A., Jellali, S., Jedidi, N., 2010. Ammonium biosorption onto sawdust: FTIR
analysis, kinetics and adsorption isotherms modeling. Bioresour. Technol. 101,
5070–5075.
Wu, F.C., Tseng, R.L., Huang, S.C., Juang, R.S., 2009. Characteristics of pseudo-second-
order kinetic model for liquid-phase adsorption: a mini-review. Chem. Eng. J.
151, 1–9.
Xu, X., Gao, B.Y., Jin, B., Yue, Q.Y., 2016. Removal of anionic pollutants from liquids by
biomass materials: a review. J. Mol. Liq. 215, 565–595.
Yoon, I.H., Meng, X., Wang, C., Kim, K.W., Bang, S., Choe, E., Lippincott, L., 2009.
Perchlorate adsorption and desorption on activated carbon and anion exchange resin.
J. Hazard. Mater. 164, 87–94.
Zularisam, A.W., Ismail, A.F., Salim, R., 2006. Behaviours of natural organic matter in
membrane filtration for surface water treatment-a review. Desalination 194,
211–231.