Chapter 4 PDF

CHAPTER-IV
RESULTS AND DISCUSSION

4.1 Characterization of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
4.1.1 XRD study
XRD patterns of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are

depicted in Figs.4.1 and 4.2. Mineralogical composition of bentonite is found to be
montmorillonite (4.48, 4.28 and 1.87 ), quartz (3.32, 2.29, 2.12, 1.90 and 1.51 )
and calcite (3.04 and 2.09 ) but kaolinite is mainly composed of quartz (4.17, 3.32
and 1.78 ), kaolinite (7.12, 4.35, 3.56, 2.49, 2.33 and 1.97) and kaolinite + quartz
(1.66 ).
XRD pattern of NPP-bentonite revealed the disappearance of quartz peaks (2 =

42.47 and 2 = 47.38) but in case of NPP-kaolinite new kaolinite peak (2 = 35.02)
was observed.
XRD patterns of both NPP-bentonite and NPP-kaolinite showed almost same

peaks as that of bentonite and kaolinite but with increased basal spacing and
decreased peak intensity. This suggests that NPP treatment has effectively modified
the surface of bentonite and kaolinite but it did not affect the crystal structure of
bentonite and kaolinite.
64
10000
Bentonite M- Montmorillonite
Q- Quartz
Q (3.32 )
8000 C- Calcite
Intensity (CPS)
6000
C (3.04 )
4000
M (4.28 )
M (4.48 )
Q (2.29 )
M (1.87 )
Q (2.12 )
C (2.09 )
Q (1.90 )
Q (1.51 )
2000
0
10 20 30 40 50 60
2 (deg)
4000
NPP-bentonite M- Montmorillonite
Q- Quartz
Q (3.36 )
3000 C- Calcite
Intensity (CPS)
C (3.05 )
M (4.29 )
M (4.50 )
C (2.10 )
2000
Q (2.29 )
M (1.88 )
Q (1.54 )
1000
0
10 20 30 40 50 60
2 (deg)
Fig.4.1 XRD patterns of bentonite and NPP-bentonite.
65
Intensity (CPS) Intensity (CPS)
0
2000
4000
6000
8000
10000
12000
14000
0
10000
2000
4000
6000
8000
10
10
K (7.18 ) K (7.12 )
K (4.37 ) K (4.35 )
Kaolinite
20
20
Q (4.20 ) Q (4.17 )
NPP-kaolinite
K (3.56 ) K (3.56 )
Q (3.34 ) Q (3.32 )
30
30
66
2 (deg)
2 (deg)
K (2.56 )
K (2.50 ) K (2.49)
K (2.34 ) K (2.33 )
40
40
K (1.99 ) K (1.97 )
50
50
Q (1.78 ) Q (1.78 )
Fig.4.2 XRD patterns of kaolinite and NPP-kaolinite.

Q- Quartz
Q- Quartz
K+Q (1.66 ) K+Q (1.66 )

K- Kaolinite
K- Kaolinite
60
60
4.1.2 XRF analysis
Chemical composition of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite

is presented in Table 4.1. XRF analysis of bentonite, kaolinite and their modified
forms revealed that SiO2 and Al2O3 are major constituents. The content of CaO (%)
was found to be higher in bentonite but kaolinite revealed higher MgO (%) content.
Presence of SiO2 (%) in NPP-bentonite and NPP-kaolinite decreased slightly as
compared to that of bentonite and kaolinite.
Table 4.1 Chemical composition of bentonite, NPP-bentonite, kaolinite and NPP-

kaolinite
Constituents Weight (%)
Bentonite NPP-bentonite Kaolinite NPP-kaolinite

SiO2 63.71 62.10 56.28 53.94
Al2O3 15.56 16.83 28.90 32.72
Fe2O3 4.29 3.67 1.73 1.05
CaO 3.32 2.98 0.26 0.18
MgO 1.73 1.35 1.42 0.86
Na2O 2.48 2.16 1.29 0.72
K2O 0.95 0.54 0.68 0.37
LOI* 7.94 10.11 9.41 9.95
LOI* - Loss on ignition
4.1.3 FTIR study
FTIR spectra of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are shown

in Figs.4.3 and 4.4. Tables 4.2 and 4.3 summarize the band position (cm-1) of
bentonite and kaolinite before modification, their shifting after NPP modification
along with possible band assignments. The band intensity of NPP-bentonite and NPP-
kaolinite was lower than that of bentonite and kaolinite.
67
Fig.4.3 FTIR spectra of bentonite and NPP-bentonite.
68
Fig.4.4 FTIR spectra of kaolinite and NPP-kaolinite.
69
Table 4.2 FTIR bands of bentonite and NPP-bentonite with possible band
assignments (Guo et al., 2012; Madejova, 2003; Tomic et al., 2011)
Band position (cm-1) Band assignment
Bentonite NPP-bentonite
3628 3636 OH stretching vibrations of structural hydroxyls
1635 1680 H-O-H bending vibrations of water molecules
1037 1032 Si-O stretching vibrations
910 906 Al-Al-OH stretching vibrations
522 512 Si-O-Al bending vibrations
463 450 Si-O-Si bending vibrations
Table 4.3 FTIR bands of kaolinite and NPP-kaolinite with possible band assignments
(Cheng et al., 2010; Madejova, 2003; Panda et al., 2010)
Band position (cm-1) Band assignment
Kaolinite NPP-kaolinite
3696 3692 OH stretching of inner surface hydroxyl.
3620 3623 OH stretching of structural hydroxyls
3430 3421 H-O-H stretching vibrations of water molecules
1634 1639 H-O-H bending vibrations of water molecules
914 908 Al-Al-OH stretching vibrations
792 794 Al-Mg-OH stretching vibrations
694 695 Si-O-Al stretching vibrations
538 536 Si-O-Al stretching vibrations
470 464 Si-O-Si bending vibrations
70
4.1.4 SEM analysis
The SEM images of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are

depicted in Figs.4.5 a, b, c and d. SEM images of bentonite and kaolinite show
smaller particles but in case of NPP-bentonite and NPP-kaolinite larger particles are
observed due to the agglomeration of smaller particles.
(a) Bentonite (b) NPP-bentonite
(c) Kaolinite (d) NPP-kaolinite
Fig.4.5 SEM images of (a) Bentonite (b) NPP-bentonite (c) Kaolinite and (d) NPP-
kaolinite.
71
4.1.5 SSA and CEC
SSA and CEC of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are

tabulated in Table 4.4. SSA of NPP-bentonite (72.60 m2/g) and NPP-kaolinite
(17.56 m2/g) are found to be higher than that of bentonite (39.00 m2/g) and kaolinite
(10.20 m2/g).
CEC of 67.37 meq/100 g for bentonite and 13.75 meq/100 g for kaolinite are
lower as compared to 136.25 meq/100 g for NPP-bentonite and 28.12 meq/100 g for
NPP-kaolinite.
Table 4.4 SSA and CEC of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
Adsorbent SSA (m2/g) CEC (meq/100 g)
Bentonite 39.00 67.37

NPP-bentonite 72.60 136.25
Kaolinite 10.20 13.75
NPP-kaolinite 17.56 28.12
4.1.6 Reaction mechanism of bentonite and kaolinite modification with sodium

pyrophosphate (NPP)
Fig.4.6 and 4.7 show the reaction mechanism of modification of bentonite and
kaolinite with sodium pyrophosphate (NPP). It is clearly seen that phosphate ions are
held on to the surface of bentonite and kaolinite.
O O O O
Na O P O P O Na B O P O P O 4Na
ONa ONa O O
(Sodium pyrophosphate) (Bentonite)
B
Fig.4.6 Reaction mechanism of modification of bentonite with sodium pyrophosphate

(NPP).
72
O O O O
Na O P O P O Na K O P O P O 4Na
ONa ONa O O
(Sodium pyrophosphate) (Kaolinite)
K
Fig.4.7 Reaction mechanism of modification of kaolinite with sodium pyrophosphate

(NPP).
73
4.2 Adsorption of As(III) by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite
4.2.1 Effect of pH
The pH has got an important role in the adsorption process because it has effect
not only on the surface charge density of the adsorbent but also on the existing form
of the adsorbate (Yu et al., 2013). The effect of pH on the adsorption of As(III) by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite is depicted in Fig.4.8.
As(III) adsorption from aqueous solutions increased with increase in pH of the

solutions. As the pH increased from 1.0 to 8.0, As(III) adsorption efficiency also
increased from 10.20 % to 53.50 %, 12.10 % to 63.10 %, 2.30 % to 32.40 % and
5.47 % to 41.60 % with bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
respectively. As(III) adsorption efficiency using NPP-bentonite and NPP-kaolinite
increased more as compared to bentonite and kaolinite which has proved that
bentonite and kaolinite have undergone modification with NPP.
At low pH of solution, As(III) exists in the form of H3 AsO3, which shifts to

H2AsO3 - as the pH increases (Su et al., 2011). At low pH, surface of clay adsorbent is
highly protonated and this results in a weak interaction between H3 AsO3 and clay
adsorbents. The only driving force between H3AsO3 and clay adsorbents is physical
adsorption which results in less adsorption. Anion exchange is not a major mechanism
as shown in equations (4.1) and (4.2) (Su et al., 2011):
X OH + H3AsO3 X HAsO3 + H2O (monodentate) (4.1)
2X OH + H3AsO3 X2 HAsO3 + 2H2O (bidentate) (4.2)
Where, X is Si or Al
At near neutral pH values (7 - 9) slow dissociation of H3 AsO3 producing Arsenite

ions begins and it reaches maximum at pH 8.0. The partially neutral and partially
negatively charged Arsenite ions get attracted to the positively charged surface of the
clay adsorbents thereby resulting in high As(III) adsorption by clay adsorbents in this
pH range (Anjum et al., 2011).
74
Similar trends have been reported for adsorption of As(III) by Ti-pillared
montmorillonite (Na et al., 2009), China clay-fly ash (Singh et al., 2009),
montmorillonite (Anjum et al., 2011) and ODBDA-modified bentonite (Su et al.,
2011).
80
As(III) adsorption (%)
60
Bentonite
40
NPP-bentonite
Kaolinite
20 NPP-kaolinite
0
0 2 4 6 8 10
pH
Fig.4.8 Effect of pH on adsorption of As(III) by bentonite, NPP-bentonite, kaolinite

and NPP-kaolinite.
4.2.2 Effect of adsorbent dose
Fig.4.9 shows the effect of dose of adsorbents on adsorption of As(III) by

bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Results showed that As(III)
adsorption efficiency by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
27.60 % to 41.60 %, respectively but corresponding As(III) adsorption capacity of
bentonite, NPP-bentonite, kaolinite and NPP kaolinite decreased from 18.30 mg/g to
8.91 mg/g, 22.91 mg/g to 10.51 mg/g, 9.00 mg/g to 5.40 mg/g and 13.80 mg/g to 6.93
mg/g, respectively with increase in dose of adsorbents from 1 g/L to 3 g/L. NPP-
bentonite and NPP-kaolinite showed increased As(III) adsorption efficiency and
adsorption capacity as compared to bentonite and kaolinite due to increase in SSA and
CEC of modified clay forms.
Increase in adsorption efficiency is attributed to the increase in surface area

which in turn increases the availability of adsorption sites on adsorbent surface
75
(Wanees et al., 2012) but decrease in adsorption capacity is due to the following
reasons (Sarma et al., 2011):
Presence of large amount of adsorbent reduces the unsaturation of the

adsorption sites and correspondingly, number of such sites per unit mass
comes down resulting in comparatively less adsorption at higher adsorbent
amount, and
Higher amount of adsorbent creates particle aggregation resulting in decrease

in total surface area of the adsorbent.
80 25
Adsorption capacity (mg/g)

Bentonite
20
60 NPP-bentonite
15 Kaolinite
40 NPP-kaolinite
10
Bentonite
20
5 NPP-bentonite
Kaolinite
0 0
NPP-kaolinite
0 2 4 6 8 10 12
Dose of adsorbents (g/L)
Fig.4.9 Effect of dose of adsorbents on adsorption of As(III) by bentonite, NPP-

bentonite, kaolinite and NPP-kaolinite.
4.2.3 Effect of contact time
Effect of contact time on adsorption of As(III) by bentonite, NPP-bentonite,

kaolinite and NPP-kaolinite is shown in Fig.4.10. It is clear that maximum As(III)
adsorption efficiency of 53.50 %, 63.10 %, 32.40 % and 41.60 % by bentonite,
NPP-bentonite, kaolinite and NPP-kaolinite respectively was achieved at 180 min. A
rapid As(III) adsorption of 51.30 %, 60.24 %, 31.74 % and 39.98 % took place in the
initial 60 min by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite respectively
but thereafter the adsorption proceeded at a slower rate until equilibrium was reached.
The reason being that, at initial stage more number of vacant adsorption sites are
available which gets occupied at later stages by As(III) ions as a result the number of
vacant adsorption sites decrease.
76
80

60
Bentonite
40
NPP-bentonite
Kaolinite
20
NPP-kaolinite
0
0 50 100 150 200 250
Contact time (min)
Fig.4.10 Effect of contact time on adsorption of As(III) by bentonite, NPP-bentonite,

kaolinite and NPP-kaolinite.
4.2.3.1 Adsorption kinetics
Pseudo-first order model and pseudo-second order model plots are shown in
Fig.4.11 and 4.12 respectively. Table 4.5 lists the kinetic parameters for As(III)
adsorption by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. It is clear from
the table that the qe cal values of pseudo-second order model are much closer to qe exp
2
values and regression coefficients (R ) are also higher for pseudo-second order model.
Therefore, it can be concluded that adsorption of As(III) by bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite followed pseudo-second order adsorption mechanism and
this suggests the involvement of chemical adsorption through exchange or sharing of
electrons between adsorbate and adsorbent (Zehhaf et al., 2012).
77
1.5
0.5
log (qe - qt) (mg/g) 0 Bentonite
0 50 100 150 200 NPP-bentonite
-0.5
-1 Kaolinite
NPP-kaolinite
-1.5
-2
-2.5
Time (min)
Fig.4.11 Pseudo-first order plots for adsorption of As(III) by bentonite, NPP-

12
10
t/qt (min g/mg)
8
Bentonite
6
NPP-bentonite
4 Kaolinite
2 NPP-kaolinite
0
0 50 100 150 200
Time (min)
Fig.4.12 Pseudo-second order plots for adsorption of As(III) by bentonite, NPP-

78
Table 4.5 Kinetic parameters for As(III) adsorption by bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite
Adsorbent Pseudo-first order model Pseudo-second order model
qe exp qe cal K1 (l/min) R2 qe cal K2 (g/mg R2

(mg/g) (mg/g) (mg/g) min)
Bentonite 8.91 7.30 2.00 x 10-2 0.985 10.00 2.97 x 10-2 0.999
NPP- 10.51 9.21 2.50 x 10-2 0.962 11.36 3.46 x 10-2 0.997
bentonite
Kaolinite 5.40 2.40 1.50 x 10-2 0.943 6.66 1.90 x 10-2 0.993
NPP- 6.93 5.20 1.76 x 10-2 0.971 8.33 2.56 x 10-2 0.995
kaolinite
4.2.4 Effect of initial As(III) concentration
The results showed that As(III) adsorption capacity by bentonite, NPP-bentonite,

kaolinite and NPP-kaolinite increased from 2.28 mg/g to 8.91 mg/g, 2.44 mg/g to
10.51 mg/g, 1.74 mg/g to 5.40 mg/g and 2.07 mg/g to 6.93 mg/g respectively as the
initial As(III) concentration increased from 10 mg/L to 50 mg/L. On the other hand,
the percent As(III) adsorption by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite decreased from 68.50 % to 53.50 %, 73.20 % to 63.10 %, 52.20 % to
32.40 % and 62.10 % to 41.60 %, respectively with increase in initial As(III)
concentration from 10 mg/L to 50 mg/L (Fig.4.13).
With increase in initial metal ion concentration the driving force of the metal ions
towards the active adsorption sites on the adsorbent increases as a result the
adsorption capacity increases. On other hand, decrease in percentage adsorption may
be due to the saturation of available active adsorption sites on the adsorbent surface
(Jiang et al., 2010; Ozdes et al., 2011).
79
80 12

10 Bentonite
60 NPP-bentonite
8
Kaolinite
40 6
NPP-kaolinite
4 Bentonite
20
2 NPP-bentonite
Kaolinite
0 0
NPP-kaolinite
0 20 40 60
Initial As(III) concentration (mg/L)
Fig.4.13 Effect of initial As(III) concentration on adsorption of As(III) by bentonite,

NPP-bentonite, kaolinite and NPP-kaolinite.
4.2.4.1 Adsorption isotherms
Figs. 4.14 and 4.15 depict the plots of Langmuir and Freundlich isotherm models.
The isotherm constants for As(III) adsorption by bentonite, NPP-bentonite, kaolinite
and NPP-kaolinite are presented in Table 4.6.
The Langmuir adsorption capacity (qm) for As(III) adsorption by tested

adsorbents is in the following order: NPP-bentonite (17.54 mg/g) > bentonite (15.15
mg/g) > NPP kaolinite (12.50 mg/g) > kaolinite (10.00 mg/g). The Langmuir
adsorption capacity for NPP-bentonite and NPP-kaolinite was found to be higher than
that for bentonite and kaolinite due to the increase in number of adsorption sites on
adsorbent surface. Comparison of Langmuir adsorption capacity (qm) of various
adsorbents for As(III) adsorption are summarized in Table 4.7.
Separation factor (RL) lies between 0 and 1 which indicates favorable adsorption
and higher regression coefficient (R2) values were achieved with Langmuir isotherm
model. This signifies that the adsorption data fitted well to Langmuir isotherm model
with As(III) adsorption taking place on monolayer for the studied adsorbents.
80
4
Ce/qe (g/L) Bentonite

2
NPP-bentonite
Kaolinite
1 NPP-kaolinite
0
0 20 40 60
Ce (mg/L)
Fig.4.14 Langmuir isotherm plots for adsorption of As(III) by bentonite, NPP-

2
log qe (mg/g)
Bentonite
1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0.9 1.2 1.5 1.8
log Ce (mg/L)
Fig.4.15 Freundlich isotherm plots for adsorption of As(III) by bentonite, NPP-

81
Table 4.6 Isotherm constants for As(III) adsorption by bentonite, NPP-bentonite,
Adsorbent Langmuir Isotherm Freundlich Isotherm
qm (mg/g) b (L/g) RL R2 Kf (mg/g)/ n R2

(mg/L)1/n
Bentonite 15.15 150.15 0.0006 0.998 1.18 0.62 0.936

NPP- 17.54 78.12 0.0012 0.999 2.08 0.71 0.954
bentonite
Kaolinite 10.00 166.66 0.0005 0.996 0.41 0.44 0.918
NPP- 12.50 160.00 0.0006 0.999 0.78 0.58 0.947
kaolinite
Table 4.7 Comparison of As(III) adsorption capacity by various adsorbents
Adsorbent qm (mg/g) Reference
HDTMA-modified kaolinite 0.32 Li et al., 2007

Al/Fe-modified montmorillonite 19.11 Ramesh et al., 2007
Ti-pillared montmorillonite 14.72 Na et al., 2009
China clay-fly ash 0.39 Singh et al., 2009
Magnetic iron oxide 55.20 Liu et al., 2010
Maize leaves 2.03 Kamsonlian et al., 2011
ODBDA-modified bentonite 0.82 Su et al., 2011
Ceria nanoparticles 18.15 Feng et al., 2012
Iron-modified bamboo charcoal 3.06 Liu et al., 2012
Cinnamomum zeylanicum bark 36.31 Al-Mamun et al., 2013
Nano-alumina powder 40.00 Darban et al., 2013
El-Haria clay 75.40 Eloussaief et al., 2013
Bentonite 15.15 Present study
NPP-bentonite 17.54 Present study
Kaolinite 10.00 Present study
NPP-kaolinite 12.50 Present study
82
4.2.5 Statistical analysis using central composite experimental design
Based on experimental results, a four-level four-variable central composite

response surface model was developed using the following equation (4.3).
Adsorption (%) = 53.69 + 4.1 x A 10.95 x B + 2.92 x C + 1.81 x D 33.66 x A2 +

0.95 x B2 8.17 x C2 2.27 x D2 0.143 x AB + 0.0794 x AC 0.143 x AD + 0.556
x BC 0.478 x BD + 0.556 x CD (4.3)
Where A, B, C and D are pH, adsorbent dose (g/L), contact time (min) and initial
As(III) concentration (mg/L), respectively.
Comparative experimental and predicted values for adsorption of As(III) by NPP-

kaolinite are presented in Table 4.8. It is clear that experimental values are closer to
predicted values. ANOVA for As(III) adsorption by NPP-kaolinite is summarized in
Table 4.9. The F-value of 45.61 at P-value of 0.05 indicates that the model is
significance.
The 3D response surface plots of effects of pH, adsorbent dose, contact time and
initial As(III) concentration for adsorption of As(III) by NPP-kaolinite are presented
in Fig.4.16.
The experimental (41.60 %) and predicted As(III) adsorption (42.18 %) using

NPP-kaolinite was found to occur under optimum conditions of pH 8.0, 3 g/L
adsorbent dose, 180 min contact time and 50 mg/L initial As(III) concentration this
indicates the accuracy of the results obtained.
83
Table 4.8 Comparative experimental and predicted values for adsorption of As(III) by
NPP-kaolinite
Standard Experimental Predicted

A B C D
order value (%) value (%)
1 1 3 180 50 5.47 5.82
2 2 3 180 50 7.51 7.46
3 3 3 180 50 10.52 10.69
4 4 3 180 50 14.69 14.83
5 5 3 180 50 19.74 19.72
6 6 3 180 50 25.83 25.00
7 7 3 180 50 32.98 32.53
8 8 3 180 50 41.60 42.18
9 8 1 180 50 27.60 26.88
10 8 2 180 50 36.08 36.21
11 8 10 180 50 41.60 42.18
12 8 3 10 50 31.20 32.37
13 8 3 20 50 35.92 35.62
14 8 3 30 50 37.84 37.81
15 8 3 40 50 38.88 38.70
16 8 3 50 50 39.54 39.36
17 8 3 60 50 39.98 40.15
18 8 3 70 50 40.32 40.30
19 8 3 80 50 40.56 40.48
20 8 3 90 50 40.76 40.64
21 8 3 100 50 40.94 40.90
22 8 3 110 50 41.06 41.00
23 8 3 120 50 41.18 41.20
24 8 3 130 50 41.28 41.26
25 8 3 140 50 41.36 41.38
26 8 3 150 50 41.42 41.53
27 8 3 160 50 41.48 41.75
28 8 3 170 50 41.54 41.96
29 8 3 240 50 41.60 42.18
30 8 3 180 10 62.10 62.89
31 8 3 180 20 55.30 55.76
32 8 3 180 30 49.83 50.10
33 8 3 180 40 45.34 45.52
84
Table 4.9 ANOVA for As(III) adsorption by NPP-kaolinite
Degree of
Source Sum of squares Mean square F value P value
freedom
Model 8 3074.0750 384.2593 45.6102 < 0.0001

Residual 35 294.8698 0.42
Total 43 3368.9440
A 1 29.1406 29.1406 3.4588 0.0413
B 1 523.5359 523.535 62.1418 < 0.0001
C 1 50.1594 50.1594 5.9537 0.0199
D 1 31.6610 31.6610 3.7580 0.0307
A2 1 938.7154 938.715 111.4222 < 0.0001
B2 1 1.1401 1.1401 0.1353 0.7152
C2 1 88.7668 88.7668 10.5363 0.0026
D2 1 14.0058 14.0058 1.6624 0.2057
85
Fig.4.16 The 3D response surface plots of effects of pH, adsorbent dose, contact time
and initial As(III) concentration for adsorption of As(III) by NPP-kaolinite.
86
4.2.6 Desorption studies
As(III) adsorption/desorption efficiencies of bentonite, NPP-bentonite, kaolinite

and NPP-kaolinite are shown in Figs.4.17 a, b, c and d. As(III) desorption efficiency
achieved with 120 min contact time using 1 M HCl was found to be 45.48 % for
bentonite, 56.10 % for NPP-bentonite, 19.28 % for kaolinite and 31.58 % for NPP-
kaolinite, respectively in the first cycle which decreased to 14.28 %, 25.12 %, 0.10 %
and 0.36 % respectively for third cycle. On the other hand, As(III) adsorption
efficiency using regenerated bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
also decreased from 53.50 % to 24.52 %, 63.10 % to 36.08 %, 32.40 % to 10.62 %
and 41.60 % to 10.62 %, respectively as the number of cycles increased from one to
three. This is due to decrease in number of adsorption sites on the surface of
adsorbents.
(a) Bentonite
Adsorption/desorption (%)
60
40
Adsorption
20
Desorption
0
1 2 3
Number of cycles
(b) NPP-bentonite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
87
(c) Kaolinite
Adsorption/desorption ( %)
40
30
20 Adsorption
10 Desorption
0
1 2 3
Number of cycles
(d) NPP-kaolinite
50
40
30
20 Adsorption
Desorption
10
0
1 2 3
Number of cycles
Fig.4.17 As(III) adsorption/desorption efficiency for (a) bentonite, (b) NPP-bentonite,

(c) kaolinite and (d) NPP-kaolinite.
88
4.2.7 Adsorption of As(III) from fertilizer wastewater using bentonite, NPP-
bentonite, kaolinite and NPP-kaolinite
The physico-chemical characteristics of fertilizer wastewater are shown in Table

4.10. Under optimum conditions of pH 8.0, 3 g/L adsorbent dose and 180 min contact
time, As(III) adsorption from fertilizer wastewater using bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite was found to be 68.13 %, 73.18 %, 50.76 % and 61.53 %
respectively. This reveals that As(III) has higher affinity towards NPP-bentonite
followed by bentonite, NPP-kaolinite and kaolinite. Even after treatment the As(III)
concentration remaining in fertilizer wastewater was above permissible limit. Hence
second cycle was applied which completely removed As(III) from fertilizer
wastewater by studied adsorbents.
Table 4.10 Physico-chemical characteristics of fertilizer wastewater
Parameters Content
pH 4.32
Electrical conductivity (s/cm) 2967
Total dissolved solids (mg/L) 1635
Calcium (mg/L) 474.8
Magnesium (mg/L) 215.1
Chloride (mg/L) 210.0
Sulphate (mg/L) 259.4
Phosphate (mg/L) 88.5
Nitrite + Nitrate (mg/L) 138.3
Sodium (mg/L) 344.6
Potassium (mg/L) 42.9
Arsenic(III) (mg/L) 4.55
Lead(II) (mg/L) 2.89
Dissolved oxygen (mg/L) Nil
Chemical oxygen demand (mg/L) 486.3
89
4.3 Adsorption of Cr(VI) by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite
4.3.1 Effect of pH
The Cr(VI) adsorption process is greatly affected by the pH of the solution

(Zhao et al., 2013). Fig.4.18 shows the effect of pH on adsorption of Cr(VI) by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Cr(VI) adsorption efficiency
by tested adsorbents decreased with increase in pH of the solution. At pH 2.0,
maximum Cr(VI) adsorption efficiency achieved was found to be 66.10 % by
bentonite, 76.50 % by NPP-bentonite, 42.70 % by kaolinite and 54.90 % by NPP-
kaolinite.
At pH 1.0, Cr(VI) adsorption efficiency decreased slightly for all the adsorbents
studied as compared to that obtained at pH 2.0 but drastic decrease in Cr(VI)
adsorption efficiency by bentonite (27.40 %), NPP-bentonite (38.60 %), kaolinite
(9.10 %) and NPP-kaolinite (15.56 %) was observed at pH 7.0. Results also showed
that NPP-bentonite and NPP-kaolinite had increased Cr(VI) adsorption efficiency to
the extent of 10 % to 12 % as compared to that of bentonite and kaolinite.
Cr(VI) in aqueous solution exists mainly in such forms as H2CrO4, HCrO4-,

CrO42-, Cr2O72-, etc depending on the pH of the solution and Cr(VI) concentration
(Doke et al., 2012). In pH range of 2.0-7.0 the dominant forms of Cr(VI) are Cr2O72-
and HCrO4 - ions, but at higher pH CrO42- ions prevail in the solution (Plaska et al.,
2010). The Cr(VI) speciation can be shown by the following reactions (Mohan et al.,
2005; Weng et al., 2008):
H2CrO4 H+ + HCrO4- (4.4)

- + 2-
HCrO4 H + CrO4 (4.5)
- +
HCrO4 H + Cr2O72- (4.6)
-
2HCrO4 Cr2O72- + H2O (4.7)
At low pH, the clay surfaces become positively charged due to strong
protonation, electrostatic force between the positively charged surface and negatively
charged HCrO4- and Cr2O72- enhance Cr(VI) adsorption by clay particles. At high pH,
surface groups partially deprotonate and the surface becomes negatively charged,
90
which in turn inhibits the Cr(VI) adsorption due to competition between Cr(VI) ions
and hydroxide ions, resulting in a decrease in Cr(VI) uptake (Hong et al., 2008).
Similar trends were reported for Cr(VI) adsorption on Readiye and Hanili clays
(Gde et al., 2010), alginate-montmorillonite/polyaniline nanocomposite (Olad and
Azhar, 2013), and Akadama clay (Zhao et al., 2013).
100
Cr(VI) adsorption (%)
80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 2 4 6 8
pH
Fig.4.18 Effect of pH on adsorption of Cr(VI) by bentonite, NPP-bentonite, kaolinite

and NPP-kaolinite.
4.3.2 Effect of absorbent dose
The effect of dose of adsorbents on adsorption of Cr(VI) by bentonite, NPP-

bentonite, kaolinite and NPP-kaolinite is shown in Fig.4.19. It is clear that Cr(VI)
adsorption capacity by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
decreased from 23.25 mg/g to 11.01 mg/g, 27.55 mg/g to 12.75 mg/g, 12.15 mg/g to
7.11 mg/g and 19.15 mg/g to 9.15 mg/g, respectively when the dose of adsorbents was
increased from 1.0 g/L to 3 g/L.
The Cr(VI) adsorption efficiency increased from 46.50 % to 66.10 %, 55.10 % to

76.50 %, 24.30 % to 42.70 % and 38.10 % to 54.90 %, with increase in bentonite,
NPP-bentonite, kaolinite and NPP-kaolinite doses respectively from 1.0 g/L to
3.0 g/L. Higher SSA and CEC for NPP-bentonite and NPP-kaolinite resulted in
increased Cr(VI) adsorption capacity and adsorption efficiency as compared to that
obtained with bentonite and kaolinite.
91
Decrease in adsorption capacity may be due to the fact that adsorption sites
remain unsaturated during the adsorption process, whereas the number of sites
available for adsorption increases by increasing the adsorbent dose (Olad and Azhar,
2013). The higher adsorption efficiency achieved could be attributed to the
availability of more number of adsorption sites as well as larger surface area for
adsorption with the increase in adsorbent doses (Zhao et al., 2013).
100 30

Bentonite
80
NPP-bentonite
20
60 Kaolinite
NPP-kaolinite
40
10 Bentonite
20 NPP-bentonite
Kaolinite
0 0
NPP-kaolinite
0 2 4 6 8 10 12
Fig.4.19 Effect of dose of adsorbents on adsorption of Cr(VI) by bentonite, NPP-

The results showed that at the first 60 min, rapid Cr(VI) adsorption of 62.72 %,
72.58 %, 40.70 % and 51.98 % by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite respectively was achieved with the equilibrium reaching at a slower rate. At
180 min, maximum Cr(VI) adsorption efficiency was achieved by bentonite,
NPP-bentonite, kaolinite and NPP-kaolinite which was found to be 66.10 %, 76.50 %,
42.70 % and 54.90 % respectively (Fig.4.20). This is attributed to large number of
vacant adsorption sites available for Cr(VI) adsorption during initial stages, but these
get occupied by Cr(VI) ions in later stages thereby decreasing the number of vacant
adsorption sites.
92
100

80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 50 100 150 200 250
Contact time (min)
Fig.4.20 Effect of contact time on adsorption of Cr(VI) by bentonite, NPP-bentonite,

Figs.4.21 and 4.22 depict the plots of pseudo-first order model and pseudo-
second order model. The values of kinetic parameters for Cr(VI) adsorption by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are summarized in Table 4.11.
It is clear that pseudo-second order rate constants (K2) for Cr(VI) adsorption by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite varied from 2.67 x 10-2 to
5.25 x 10-2 g/mg min. These values indicate that Cr(VI) adsorption was rapid in case
of NPP-bentonite but slowest with respect to kaolinite.
Pseudo-second order model showed higher regression coefficient (R2) values and
closer qe cal values with qe exp values suggesting that Cr(VI) adsorption by bentonite,
NPP-bentonite, kaolinite and NPP-kaolinite followed pseudo-second order model.
These indicate the involvement of chemical adsorption through exchange or sharing
of electrons between adsorbate and adsorbent (Zehhaf et al., 2012).
93
1.5
log (qe - qt) (mg/g)

0.5
0 Bentonite
-0.5
0 50 100 150 200 NPP-bentonite
Kaolinite
-1
NPP-kaolinite
-1.5
-2
-2.5
Time (min)
Fig.4.21 Pseudo-first order plots for adsorption of Cr(VI) by bentonite, NPP-

10
8
t/qt (min g/mg)
6
Bentonite
NPP-bentonite
4
Kaolinite
2 NPP-kaolinite
0
0 50 100 150 200
Time (min)
Fig.4.22 Pseudo-second order plots for adsorption of Cr(VI) by bentonite, NPP-

94
Table 4.11 Kinetic parameters for Cr(VI) adsorption by bentonite, NPP-bentonite,

Bentonite 11.01 10.50 2.50 x 10-2 0.966 11.35 3.52 x 10-2 0.999
NPP- 12.75 11.80 3.07 x 10-2 0.972 13.33 5.25 x 10-2 0.999
bentonite
Kaolinite 7.11 6.35 1.87 x 10-2 0.983 7.69 2.67 x 10-2 0.998
NPP- 9.15 9.05 2.14 x 10-2 0.930 9.17 3.01 x 10-2 0.999
kaolinite
4.3.4 Effect of initial Cr(VI) concentration
The effect of initial Cr(VI) concentration on adsorption of Cr(VI) by bentonite,

NPP-bentonite, kaolinite and NPP-kaolinite is shown in Fig.4.23. The results showed
that percentage Cr(VI) adsorption by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite decreased from 82.20 % to 66.10 %, 86.70 % to 76.50 %, 62.20 % to 42.70
% and 77.10 % to 54.80 %, with increase in initial Cr(VI) concentration from 10
mg/L to 50 mg/L respectively.
The Cr(VI) adsorption capacity by bentonite, NPP-bentonite, kaolinite and NPP-

kaolinite increased from 2.74 mg/g to 11.01 mg/g, 2.89 mg/g to 12.75 mg/g, 2.07
mg/g to 7.11 mg/g and 2.57 mg/g to 9.15 mg/g, respectively with increase in initial
Cr(VI) concentration from 10 mg/L to 50 mg/L.
At higher initial metal ion concentration, decrease in percent adsorption was

observed which may be attributed to saturation of available adsorption sites on the
clay. Though decrease in percent adsorption was observed, increase in adsorption
capacity was due to higher driving force of metal ions toward active sites present on
the clay (Kumric et al., 2013).
95
100 14

12
Bentonite
80
10 NPP-bentonite
60 8 Kaolinite
6 NPP-kaolinite
40
Bentonite
4
20 NPP-bentonite
2
Kaolinite
0 0 NPP-kaolinite
0 20 40 60
Initial Cr(VI) concentration (mg/L)
Fig.4.23 Effect of initial Cr(VI) concentration on adsorption of Cr(VI) by bentonite,

Langmuir and Freundlich isotherm plots are presented in Figs.4.24 and 4.25.
Table 4.12 lists the isotherm constants for adsorption of Cr(VI) by bentonite, NPP-
bentonite, kaolinite and NPP-kaolinite. Cr(VI) adsorption by NPP-bentonite and NPP-
kaolinite showed maximum Langmuir adsorption capacity (qm) of 20.00 mg/g and
15.15 mg/g, respectively which were higher than the values obtained for bentonite
(17.54 mg/g) and kaolinite (12.50 mg/g). This suggests that modification of bentonite
and kaolinite with NPP has effectively increased the number of adsorption sites to a
large extent.
Comparison of Langmuir adsorption capacity (qm) of various adsorbents for

Cr(VI) adsorption are made in Table 4.13. Favorable Cr(VI) adsorption by bentonite,
NPP-bentonite, kaolinite and NPP-kaolinite was confirmed by separation factor (RL)
values (< 1). Langmuir isotherm model showed higher regression coefficient (R2)
values than that of Freundlich isotherm model values which suggest that experimental
data fitted well to Langmuir isotherm model. Therefore, it can concluded that Cr(VI)
adsorption by tested adsorbents takes place on monolayer.
96
3
2
NPP-bentonite
1 Kaolinite
NPP-kaolinite
0
0 20 40 60
Ce (mg/L)
Fig.4.24 Langmuir isotherm plots for adsorption of Cr(VI) by bentonite, NPP-

2
log qe (mg/g)
Bentonite
1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0.9 1.2 1.5 1.8
log Ce (mg/L)
Fig.4.25 Freundlich isotherm plots for adsorption of Cr(VI) by bentonite, NPP-

97
Table 4.12 Isotherm constants for Cr(VI) adsorption by bentonite, NPP-bentonite,

(mg/L)1/n
Bentonite 17.54 90.49 0.0011 0.993 3.19 0.95 0.956

NPP- 20.00 125.00 0.0007 0.999 3.28 0.83 0.977
bentonite
Kaolinite 12.50 114.28 0.0008 0.999 1.01 0.50 0.902
NPP- 15.15 122.24 0.0008 0.999 2.08 0.71 0.939
kaolinite
Table 4.13 Comparison of Cr(VI) adsorption capacity by various adsorbents
Polyvinylpyridine-modified bentonite 29.85 Mansri et al., 2009

Montmorillonite-supported magnetite 15.30 Yuan et al., 2009
nanoparticles
Readiye clay 0.035 Gde et al., 2010
HDTMA-modified red clay 4.30 Plaska et al., 2010
Kaolinite 0.57 Ajouyed et al., 2011
Almond green hull 2.04 Sahranavard et al., 2011
Bentonite supported nZVI 16.67 Shi et al., 2011
Brick kiln chimney Waste 38.75 Hussain et al., 2013
Formaldehyde-treated sunflower head 7.90 Jain et al., 2013
waste
Micelle-clay 9.43 Qurie et al., 2013
Acid-activated peanut shell 46.73 Zeid et al., 2013
Akadama clay 4.29 Zhao et al., 2013
98
Equation (4.8) was used to develop central composite response surface model
using the results obtained experimentally.
Adsorption (%) = 60.183 19.688 x A 11.41 x B + 2.603 x C + 3.742 x D 11.271

x A2 + 1.369 x B2 10.230 x C2 5.656 x D2 + 0.667 x AB 0.37 x AC + 0.319 x AD
+ 0.556 x BC 0.478 x BD + 0.266 x CD (4.8)
Where, A is pH, B is adsorbent dose (g/L), C is contact time (min) and D is initial
Cr(VI) concentration (mg/L).
Table 4.14 shows the comparison made between experimental and predicted
values for Cr(VI) adsorption by NPP-kaolinite. It is clear that both experimental and
predicted values are closer to each other. Table 4.15 presents ANOVA for adsorption
of Cr(VI) by NPP-kaolinite. Significance of the model was confirmed by F-value
(65.64) at P-value 0.05.
Fig.4.26 shows the 3D response surface plots for optimum levels of pH,
adsorbent dose, contact time and initial Cr(VI) concentration for maximum adsorption
of Cr(VI) by NPP-kaolinite. At pH 2.0, adsorbent dose of 3 g/L, contact time of 180
min and initial Cr(VI) concentration of 50 mg/L showed maximum Cr(VI) adsorption
of 54.90 % (experimental) and 54.59 % (predicted) by NPP-kaolinite. This suggests
that the experimental results obtained are highly accurate.
99
Table 4.14 Comparison of experimental and predicted values for Cr(VI) adsorption
by NPP-kaolinite

A B C D
1 1 3 180 50 53.34 53.25
2 2 3 180 50 54.90 54.59
3 3 3 180 50 50.89 50.96
4 4 3 180 50 46.02 46.10
5 5 3 180 50 37.67 37.84
6 6 3 180 50 27.78 27.61
7 7 3 180 50 15.56 15.49
8 2 1 180 50 38.10 38.03
9 2 2 180 50 48.60 48.52
10 2 10 180 50 54.90 54.59
11 2 3 10 50 36.80 36.91
12 2 3 20 50 44.64 44.34
13 2 3 30 50 48.02 47.89
14 2 3 40 50 49.92 50.00
15 2 3 50 50 51.14 51.29
16 2 3 60 50 51.98 51.83
17 2 3 70 50 52.62 52.60
18 2 3 80 50 53.10 53.01
19 2 3 90 50 53.46 53.39
20 2 3 100 50 53.76 53.64
21 2 3 110 50 54.02 53.81
22 2 3 120 50 54.22 54.01
23 2 3 130 50 54.40 54.23
24 2 3 140 50 54.54 54.35
25 2 3 150 50 54.66 54.46
26 2 3 160 50 54.78 54.50
27 2 3 170 50 54.88 54.54
28 2 3 240 50 54.90 54.59
29 2 3 180 10 77.10 77.23
30 2 3 180 20 70.00 70.14
31 2 3 180 30 64.13 64.05
32 2 3 180 40 59.15 59.10
100
Table 4.15 ANOVA for adsorption of Cr(VI) by NPP-kaolinite
Degree of
freedom
Model 8 3757.825 469.7281 65.6421 < 0.0001

Residual 34 243.3004 7.1558
Total 42 4001.125
A 1 2058.749 2058.749 287.6997 < 0.0001
B 1 567.5922 567.5922 79.3181 < 0.0001
C 1 39.5940 39.5940 5.5330 0.0246
D 1 138.6273 138.6273 19.372 0.0001
A2 1 131.7505 131.7505 18.4114 0.0001
B2 1 2.3592 2.3592 0.3296 0.5696
C2 1 138.9619 138.9619 19.4192 < 0.0001
D2 1 82.9459 82.9459 11.5912 0.0017
101
and initial Cr(VI) concentration for adsorption of Cr(VI) by NPP-kaolinite.
102
Results showed that increasing the number of cycles from one to three decreased
the Cr(VI) desorption efficiency from 58.12 % to 29.04 %, 70.56 % to 41.64 %, 30.82
% to 0.76 % and 45.88 % to 15.96 % for bentonite, NPP-bentonite, kaolinite and
NPP-kaolinite, respectively in the optimum time of 120 min (Figs.4.27 a, b, c and d).
In third cycle, regenerated NPP-bentonite showed Cr(VI) adsorption efficiency of
51.48 % followed by 39.98 % for regenerated bentonite, 26.72 % for regenerated
NPP-kaolinite and 12.86 % for regenerated kaolinite. This could be attributed to the
decrease in number of adsorption sites on the surface of adsorbents.
(a) Bentonite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
(b) NPP-bentonite
100
80
60
Adsorption
40
Desorption
20
0
1 2 3
Number of cycles
103
(c) Kaolinite
50
40
30
20 Adsorption
Desorption
10
0
1 2 3
Number of cycles
(d) NPP-kaolinite
60
40
Adsorption
20
Desorption
0
1 2 3
Number of cycles
Fig.4.27 Cr(VI) adsorption/desorption efficiency for (a) bentonite, (b) NPP-bentonite,

104
4.3.7 Adsorption of Cr(VI) from electroplating wastewater using bentonite, NPP-
Table 4.16 shows the physico-chemical characteristics of electroplating

wastewater. Maximum Cr(VI) adsorption from electroplating wastewater was
80.16 % for bentonite, 85.52 % for NPP-bentonite, 58.53 % for kaolinite and 73.73 %
for NPP-kaolinite obtained at pH 2.0, with 3 g/L adsorbent dose and 180 min contact
time. Higher Cr(VI) adsorption efficiency was achieved with NPP-bentonite, and
NPP-kaolinite efficiency was 15 % more than that of kaolinite. This reveals Cr(VI)
affinity towards both NPP-bentonite and NPP-kaolinite than that of bentonite and
kaolinite. Results also showed that NPP-bentonite was able to reduce concentration of
Cr(VI) in electroplating wastewater to below permissible limit but in case of other
tested adsorbents second cycle was required to reduce Cr(VI) concentration in
electroplating wastewater to below permissible limit.
Table 4.16 Physico-chemical characteristics of electroplating wastewater
Parameters Content
pH 2.70
Sodium (mg/L) 70.3
Potassium (mg/L) 2.5
Nickel(II) (mg/L) 43.00
Chromium(VI) (mg/L) 12.30
Dissolved oxygen (mg/L) 0.17
Chemical oxygen demand (mg/L) 120
105
4.4 Adsorption of Ni(II) by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite
4.4.1 Effect of pH
The initial pH of the solution is one of the significant parameters for Ni(II)
adsorption. The adsorption efficiency of Ni(II) by bentonite, NPP-bentonite, kaolinite
and NPP-kaolinite increased with increase in the solution pH from 1.0 to 6.0 with
adsorption rate increasing from 11.70 % to 75.60 %, 14.50 % to 87.30 %, 7.10 % to
53.70 % and 8.61 % to 65.20 %, respectively (Fig.4.28). Further increase in pH of the
solution to 7.0 showed negligible increase. Therefore pH 6.0 was selected for all
further studies. Results also revealed that NPP-bentonite and NPP-kaolinite showed
higher Ni(II) adsorption efficiency as compared to bentonite and kaolinite.
At lower pH, adsorption of Ni(II) is less due to complete coverage of H3O+ ions
on clay surface and this poses difficulty for Ni(II) ions to compete for adsorption
sites. When pH increases number of H3O+ ions decreases and as a result Ni(II) ions
get adsorbed onto free available sites of adsorbents (Gupta and Bhattacharyya, 2006).
Similar trends have been reported for adsorption of Ni(II) by bentonite (Suresh et al.,
2009), Egyptian kaolin, Ca-bentonite and Na-bentonite (Talaat et al., 2011), and
Maghnite (Zenasni et al.,2013).
100
Ni(II) adsorption (%)
80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 2 4 6 8
pH
Fig.4.28 Effect of pH on adsorption of Ni(II) by bentonite, NPP-bentonite, kaolinite

and NPP-kaolinite.
106
Fig.4.29 shows the effect of dose of adsorbents on adsorption of Ni(II) by

bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. The results demonstrated that
increase in dose of adsorbents from 1 g/L to 2 g/L increased the Ni(II) adsorption
efficiency from 61.20 % to 75.60 % for bentonite, 72.60 % to 87.30 % for NPP-
bentonite, 37.40 % to 53.70 % for kaolinite and 51.00 % to 65.20 % for NPP-kaolinite
but Ni(II) adsorption capacity decreased from 30.60 mg/g to 18.90 mg/g, 36.30 mg/g
to 21.82 mg/g, 18.70 mg/g to 13.42 mg/g and 25.50 mg/g to 16.30 mg/g for bentonite,
NPP-bentonite, kaolinite and NPP-kaolinite, respectively. NPP-bentonite and NPP-
kaolinite showed higher adsorption efficiency and adsorption capacity of Ni(II) due to
increase in their SSA and CEC compared to bentonite and kaolinite.
Increase in adsorption efficiency is due to the fact that for a fixed metal ion
concentration, higher adsorbent doses mean availability of larger surface area or
larger number of adsorption sites. Decrease in adsorption capacity may be due to
(Alandis et al., 2010):
When the adsorbent dose is small, the metal ions can easily access the
adsorption sites and adsorption capacity is high. With increasing adsorbent
dose, the corresponding increase in adsorption capacity is less because the
metal ions find it difficult to approach the adsorption sites due to
overcrowding of clay mineral particles termed as solid concentration effect,
and
Higher adsorbent dose creates particle aggregation, resulting in decrease in the

total surface area.
107
100 40

Bentonite
80
30
NPP-bentonite
60 Kaolinite
20
NPP-kaolinite
40
Bentonite
10 NPP-bentonite
20
Kaolinite
0 0 NPP-kaolinite
0 2 4 6 8 10 12
Fig.4.29 Effect of dose of adsorbents on adsorption of Ni(II) by bentonite, NPP-

The effect of contact time on adsorption of Ni(II) by bentonite, NPP-bentonite,

kaolinite and NPP-kaolinite is depicted in Fig.4.30. It is clear that rapid Ni(II)
adsorption of 70.32 %, 80.52 %, 50.14 % and 60.56 % by bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite respectively was achieved in the initial 60 min time and
thereafter adsorption proceeded at a slower rate until equilibrium was attained.
Maximum Ni(II) adsorption of 75.60 % for bentonite, 87.30 % for NPP-bentonite,
53.70 % for kaolinite and 65.20 % for NPP-kaolinite was achieved at 120 min. This
may be attributed the fact that, at initial stage more number of vacant adsorption sites
are available on adsorbent surface which get occupied by Ni(II) ions at later stages as
a result the number of vacant adsorption sites decrease.
108
100

80
60
Bentonite
40 NPP-bentonite
Kaolinite
20 NPP-kaolinite
0
0 50 100 150 200
Contact time (min)
Fig.4.30 Effect of contact time on adsorption of Ni(II) by bentonite, NPP-bentonite,

Kinetic plots of pseudo-first order model and pseudo-second order model are
shown in Figs.4.31 and 4.32. Kinetic parameters values for adsorption of Ni(II) by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are tabulated in Table 4.17.
Results revealed that pseudo-second order rate constants (K2) for Ni(II) adsorption by
NPP-bentonite are higher (7.50 x 10-2 g/mg min) followed by bentonite (6.36 x 10-2
g/mg min), NPP-kaolinite (4.95 x 10-2 g/mg min) and kaolinite (3.47 x 10-2 g/mg min).
This suggests that Ni(II) adsorption by NPP-bentonite took place twice faster than that
of kaolinite. Closer qe cal and qe exp values, and higher regression coefficient (R2)
values suggest that equilibrium data fitted well to pseudo-second order model which
confirms the involvement of chemical adsorption through exchange or sharing of
electrons between adsorbate and adsorbent (Zehhaf et al., 2012).
109
2
1.5

1
Bentonite
0.5 NPP-bentonite
Kaolinite
0 NPP-kaolinite
0 50 100 150
-0.5
-1
Time (min)
Fig.4.31 Pseudo-first order plots for adsorption of Ni(II) by bentonite, NPP-bentonite,

4
t/qt (min g/mg)
3 Bentonite
NPP-bentonite
2
Kaolinite
1 NPP-kaolinite
0
0 50 100 150
Time (min)
Fig.4.32 Pseudo-second order plots for adsorption of Ni(II) by bentonite, NPP-

110
Table 4.17 Kinetic parameters for Ni(II) adsorption by bentonite, NPP-bentonite,

Bentonite 18.90 15.10 3.15 x 10-2 0.980 20.00 6.36 x 10-2 0.999
NPP- 21.82 20.64 3.52 x 10-2 0.976 22.72 7.50 x 10-2 0.998
bentonite
Kaolinite 13.42 11.89 2.14 x 10-2 0.989 13.88 3.47 x 10-2 0.999
NPP- 16.30 13.95 2.72 x 10-2 0.973 16.66 4.95 x 10-2 0.999
kaolinite
4.4.4 Effect of initial Ni(II) concentration
Fig.4.33 depict the effect of Ni(II) adsorption by bentonite, NPP-bentonite,

kaolinite and NPP-kaolinite as influenced by initial Ni(II) concentration. Results
showed that Ni(II) adsorption capacity by bentonite, NPP-bentonite, kaolinite and
NPP-kaolinite increased from 4.66 mg/g to 18.90 mg/g, 4.89 mg/g to 21.82 mg/g,
3.81 mg/g to 13.42 mg/g, and 4.46 mg/g to 16.30 mg/g, respectively but
corresponding adsorbents percentage Ni(II) adsorption decreased from 93.20 % to
75.60 % for bentonite, 97.90 % to 87.30 % for NPP-bentonite, 76.20 % to 53.70 % for
kaolinite and 89.20 % to 65.20 % for NPP-kaolinite when the initial Ni(II)
concentration in the solution was increased from 10 mg/L to 50 mg/L. This is due to
the fact that increased Ni(II) concentration accelerates the diffusion of Ni(II) ions
from solution to the adsorbent surface due to the increase in driving force of
concentration gradient and this results in increased Ni(II) adsorption capacity
(Zenasni et al., 2013). Decrease in percentage Ni(II) adsorption may be attributed to
saturation of adsorption sites on adsorbent surface (Jiang et al., 2010).
111
100 25

Bentonite
80 20
NPP-bentonite
60 15 Kaolinite
NPP-kaolinite
40 10
Bentonite
20 5 NPP-bentonite
Kaolinite
0 0
NPP-kaolinite
0 20 40 60
Initial Ni(II) concentration (mg/L)
Fig.4.33 Effect of initial Ni(II) concentration on adsorption of Ni(II) by bentonite,

The plots of Langmuir isotherm model and Freundlich isotherm model are shown
in Figs.4.34 and 4.35. The values of isotherm constants for Ni(II) adsorption by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are presented in Table 4.18. It
is clear that Langmuir adsorption capacity (qm) for Ni(II) adsorption is 27.77 mg/g for
bentonite, 30.30 mg/g for NPP-bentonite, 18.86 mg/g for kaolinite and 22.72 mg/g for
NPP-kaolinite. This points out the higher Langmuir adsorption capacity (qm) for NPP-
bentonite and NPP-kaolinite, which is due to large availability of adsorption sites as
compared to that of bentonite and kaolinite. Comparative values of Langmuir
adsorption capacity (qm) of various adsorbents for Ni(II) adsorption are summarized
in Table 4.19.
Separation factor (RL) values of less than one confirms favorable Ni(II)
adsorption by tested adsorbents. The regression coefficient (R2) values of Langmuir
isotherm model is higher than that of Freundlich isotherm model for Ni(II) adsorption
by bentonite, kaolinite and NPP-kaolinite. But in case of Ni(II) adsorption by NPP-
bentonite both Langmuir and Freundlich isotherm models showed higher regression
coefficient (R2) values. This suggests that Ni(II) adsorption by bentonite, kaolinite
and NPP-kaolinite takes place on monolayer whereas both monolayer and multilayer
adsorption pattern is applicable for Ni(II) adsorption by NPP-bentonite.
112
2

1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0 20 40 60
Ce (mg/L)
Fig.4.34 Langmuir isotherm plots for adsorption of Ni(II) by bentonite, NPP-

2
log qe (mg/g)
Bentonite
1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0.9 1.2 1.5 1.8
log Ce (mg/L)
Fig.4.35 Freundlich isotherm plots for adsorption of Ni(II) by bentonite, NPP-

113
Table 4.18 Isotherm constants for Ni(II) adsorption by bentonite, NPP-bentonite,

(mg/L)1/n
Bentonite 27.77 81.90 0.0012 0.999 3.28 0.83 0.969
NPP- 30.30 89.20 0.0011 0.999 3.98 0.90 0.999
bentonite
Kaolinite 18.86 93.02 0.0010 0.999 1.18 0.62 0.955
NPP- 22.72 66.71 0.0014 0.999 2.69 0.90 0.981
kaolinite
Table 4.19 Comparison of Ni(II) adsorption capacity by various adsorbents
Acid-activated kaolinite 11.90 Bhattacharyya and Gupta, 2008

d
Na-bentonite 13.96 Liu and Zhou, 2010
Waste acron of Quercus ithaburensis 9.42 Malkoc and Nuhoglue, 2010
Iron oxide-modified bentonite 27.93 Mockoviakov et al., 2010
Expanded perlite 2.24 Mostaedi et al., 2010
Corn cob ash 107.40 Singh and Rattan, 2011
Khulays acid-activated bentonite 47.62 Al-Shahrani, 2012
Thespesia populnea bark 54.34 Prabakaran and Arivoli, 2012
Moringa stenopetala seed 1.28 Aregawi and Mengistie, 2013
Nanosized graphite carbon-calcium 78.74 Cho et al., 2013
alginate bead
Iron oxide nanoparticles 0.23 Salmani et al., 2013
Nano hydroxyapatite 2.27 Zamani et al., 2013
114
Experimental results along with equation (4.9) were used for the development of
central composite response surface model.
Adsorption (%) = 49.8127 + 28.730 x A 12.731 x B + 0.944 x C + 8.494 x D 1.763

x A2 + 1.059 x B2 4.49 x C2 7.679 x D2 0.138 x AB + 0.778 x AC 0.294 x AD
+ 0.778 x BC 0.294 x BD + 0.229 x CD (4.9)
Where, A, B, C, and D are pH, adsorbent dose (g/L), contact time (min) and initial
Ni(II) concentration (mg/L), respectively.
Experimental and predicted values for Ni(II) adsorption by NPP-kaolinite are

shown in Table 4.20. Experimental values are closer to predicted values. Table 4.21
summarizes ANOVA for Ni(II) adsorption by NPP-kaolinite. Higher F-value of 76.47
at P-value of 0.05 confirms the significance of the model.
The 3D response surface plots of effects of pH, adsorbent dose, contact time and
initial Ni(II) concentration for adsorption of Ni(II) by NPP-kaolinite are shown in
Fig.4.36.
The optimum pH, adsorbent dose, contact time and initial Ni(II) concentration
were 6.0, 2 g/L, 120 min and 50 mg/L respectively which proved Ni(II) adsorption
efficiency of 65.20 % (experimental) is almost equal to 65.03 % (predicted) by NPP-
kaolinite. This shows that results obtained are accurate.
115
Table 4.20 Experimental and predicted values for Ni(II) adsorption by NPP-kaolinite

A B C D
1 1 2 120 50 8.61 8.72
2 2 2 120 50 17.97 17.94
3 3 2 120 50 27.54 27.66
4 4 2 120 50 38.62 38.64
5 5 2 120 50 52.13 52.00
6 6 2 120 50 65.20 65.03
7 7 2 120 50 65.30 65.03
8 6 1 120 50 51.00 49.91
9 6 10 120 50 65.20 65.03
10 6 2 10 50 37.30 37.45
11 6 2 20 50 47.10 47.16
12 6 2 30 50 53.04 53.00
13 6 2 40 50 56.56 56.78
14 6 2 50 50 58.88 58.97
15 6 2 60 50 60.56 60.50
16 6 2 70 50 61.80 61.73
17 6 2 80 50 62.80 62.88
18 6 2 90 50 63.58 63.56
19 6 2 100 50 64.20 64.38
20 6 2 110 50 64.82 64.94
21 6 2 180 50 65.20 65.03
22 6 2 120 10 89.20 89.37
23 6 2 120 20 81.35 81.48
24 6 2 120 30 75.00 74.86
25 6 2 120 40 69.72 69.53
116
Table 4.21 ANOVA for Ni(II) adsorption by NPP-kaolinite
Degree of
freedom
Model 8 8518.77 1064.846 76.473 < 0.0001

Residual 28 389.8833 13.924
Total 36 8908.654
A 1 3870.208 3870.208 277.9443 < 0.0001
B 1 693.8341 693.8341 49.8286 < 0.0001
C 1 6.037807 6.0378 0.4336 0.0451
D 1 505.4745 505.4745 36.3013 < 0.0001
A2 1 6.6867 6.6867 0.4802 0.4940
B2 1 1.3956 1.3956 0.1002 0.7539
C2 1 28.2942 28.2942 2.0319 0.1651
D2 1 135.2884 135.2884 9.7159 0.0042
117
Fig.4.36The 3D response surface plots of effects of pH, adsorbent dose, contact time
and initial Ni(II) concentration for adsorption of Ni(II) by NPP-kaolinite.
118
Figs.4.37 a, b, c and d shows Ni(II) adsorption/desorption efficiencies for

bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Results show that with 60 min
contact time, Ni(II) desorption efficiency for bentonite, NPP-bentonite, kaolinite and
NPP-kaolinite decreased from 67.72 % to 41.08 %, 82.38 % to 56.90 %, 44.26 % to
15.48 % and 54.00 % to 26.18 %, respectively when the number of cycles increased
from one to three. On other hand, Ni(II) adsorption efficiency also decreased from
75.60 % to 50.36 % for regenerated bentonite, 87.30 % to 65.20 % for regenerated
NPP-bentonite, 53.70 % to 23.52 % for regenerated kaolinite and 65.20 % to 38.04 %
for regenerated NPP-kaolinite with increase in number of cycles from one to three.
This is due to decrease in number of adsorption sites on the surface of adsorbents.
(a) Bentonite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
(b) NPP-bentonite
100
80
60
40 Adsorption
20 Desorption
0
1 2 3
Number of cycles
119
(c) Kaolinite
60
40
Adsorption
20
Desorption
0
1 2 3
Number of cycles
(d) NPP-kaolinite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
Fig.4.37 Ni(II) adsorption/desorption efficiency for (a) bentonite, (b) NPP-bentonite,

120
4.4.7 Adsorption of Ni(II) from electroplating wastewater using bentonite, NPP-
The physico-chemical characteristics of electroplating wastewater are similar to

that mentioned in Table 4.16. At pH 6.0, with 2 g/L adsorbent dose and 120 min
contact time, Ni(II) adsorption from electroplating wastewater by tested adsorbents
was in the following order: 88.74 % (NPP bentonite) > 77.69 % (bentonite) > 67.00 %
(NPP-kaolinite) > 54.90 % (kaolinite).
These results clearly show that Ni(II) adsorption by NPP-bentonite and NPP-
kaolinite was higher compared to that obtained by bentonite and kaolinite and this
suggests higher Ni(II) affinity towards NPP-bentonite and NPP-kaolinite. Second
cycle ensured complete removal of Ni(II) from electroplating wastewater by the
adsorbents used.
121
4.5 Adsorption of Pb(II) by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite
4.5.1 Effect of pH
The pH of an aqueous solution strongly affects the adsorption of heavy metals

onto clay minerals (Kumric et al., 2013). The effect of pH on adsorption of Pb(II) by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite is shown in Fig.4.38. It is clear
that Pb(II) adsorption efficiency increased from 18.20 % to 87.00 % for bentonite,
27.00 % to 98.80 % for NPP-bentonite, 12.30 % to 64.00 % for kaolinite and 13.30 %
to 76.00 % for NPP-kaolinite with increase in pH of solutions from 1.0 to 5.0 and
thereafter decreased at pH 6.0. This indicated that Pb(II) adsorption onto NPP-
bentonite and NPP-kaolinite was 12 % higher than on bentonite and kaolinite.
At lower pH values, the active sites of clay are positively charged leading to
increase in the competition between protons and Pb(II) cations for the exchangeable
sites on the adsorbents. As pH increases, this competition decreases and the sites of
the clay become more negatively charged and this favors Pb(II) adsorption through
electrostatic attraction (Zehhaf et al., 2012).
Similar trends have been reported for Pb(II) adsorption by granular bentonite
(Nava et al., 2011), natural clay (Zhang et al., 2012), and kaolinite (Ghogomu et al.,
2013).
100
Pb(II) adsorption (%)
80
60 Bentonite
40 NPP-bentonite
Kaolinite
20
NPP-kaolinite
0
0 2 4 6 8
pH
Fig.4.38 Effect of pH on adsorption of Pb(II) by bentonite, NPP-bentonite, kaolinite

and NPP-kaolinite.
122
Results showed that Pb(II) adsorption capacity by bentonite, NPP-bentonite,

kaolinite and NPP-kaolinite decreased from 38.55 mg/g to 21.75 mg/g, 46.00 mg/g to
24.70 mg/g, 24.20 mg/g to 16.00 mg/g and 31.00 mg/g to 19.00 mg/g, respectively
but corresponding Pb(II) adsorption efficiency by bentonite, NPP-bentonite, kaolinite
and NPP-kaolinite increased from 77.10 % to 87.00 %, 92.00 % to 98.80 %, 48.40 %
to 64.00 % and 62.00 % to 76.00 % with increase in dose of adsorbents from 1 g/L to
2 g/L (Fig.4.39). Both adsorption capacity and adsorption efficiency of Pb(II) by
NPP-bentonite and NPP-kaolinite increased more as compared to bentonite and
kaolinite due to larger SSA and CEC for NPP-bentonite and NPP-kaolinite
respectively.
Decrease in adsorption capacity is firstly due to the decrease in total surface area
of the adsorbent, which is the result of aggregation of clay particles. Secondly, at
constant volume of adsorbate, there is increase in the solid/liquid ratio which leaves
many sites unoccupied during adsorption process and hence there is reduced
adsorption capacity of the adsorbent. However, increase in adsorption efficiency
could be attributed to the increase in surface negative charge and decrease in
electrostatic potential near the solid surface that favors solid-solute interaction
(Owolabi et al., 2010).
100 50
80 40 Bentonite
NPP-bentonite
60 30 Kaolinite
NPP-kaolinite
40 20
Bentonite
20 10 NPP-bentonite
Kaolinite
0 0 NPP-kaolinite
0 2 4 6 8 10 12
Fig.4.39 Effect of dose of adsorbents on adsorption of Pb(II) by bentonite, NPP-

123
Fig.4.40 depict the effect of contact time on adsorption of Pb(II) by bentonite,

NPP-bentonite, kaolinite and NPP-kaolinite. It is evident that 60 min duration was
sufficient to achieve maximum Pb(II) adsorption by bentonite (87.00 %), NPP-
bentonite (98.80 %), kaolinite (64.00 %) and NPP-kaolinite (76.00 %). Pb(II)
adsorption was rapid in the first 30 min which was found to be 78.42 % for bentonite,
90.48 % for NPP-bentonite, 55.60 % for kaolinite and 68.18 % for NPP-kaolinite with
equilibrium attaining at a slower rate. This may be attributed to large number of
vacant adsorption sites which are available for Pb(II) adsorption during initial stages,
which get occupied by Pb(II) ions at later stages and this process in turn decreases the
number of vacant adsorption sites.
100
80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 50 100 150
Contact time (min)
Fig.4.40 Effect of contact time on adsorption of Pb(II) by bentonite, NPP-bentonite,

Figs.4.41 and 4.42 show the kinetic plots of pseudo-first order model and pseudo-
second order model respectively. Table 4.22 presents the values of kinetic parameters
for Pb(II) adsorption by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. The
pseudo-second order rate constants (K2) for Pb(II) adsorption by tested adsorbents
were found to be in the following order: 10.24 x 10-2 g/mg min (NPP-bentonite) >
7.55 x 10-2 g/mg min (bentonite) > 6.94 x 10-2 g/mg min (NPP-kaolinite) > 5.42 x 10-2
124
g/mg min (kaolinite). This reveals that Pb(II) adsorption by NPP-bentonite and NPP-
kaolinite was faster than that of bentonite and kaolinite.
Pseudo-second order model reveals better agreement of qe cal and qe exp values
2
along with higher regression coefficient (R ) values. This suggests that, pseudo-
second order model fitted the kinetic data of Pb(II) onto bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite better than pseudo-first order model. This implies the
involvement of chemical adsorption process through exchange or sharing of electrons
between adsorbate and adsorbent (Zehhaf et al., 2012).
1.5
1
Bentonite
0.5 NPP-bentonite
Kaolinite
0 NPP-kaolinite
0 20 40 60
-0.5
Time (min)
Fig.4.41 Pseudo-first order plots for adsorption of Pb(II) by bentonite, NPP-bentonite,

2
t/qt (min g/mg)
Bentonite
1 NPP-bentonite
Kaolinite
NPP-kaolinite
0
0 20 40 60 80
Time (min)
Fig.4.42 Pseudo-second order plots for adsorption of Pb(II) by bentonite, NPP-

125
Table 4.22 Kinetic parameters for Pb(II) adsorption by bentonite, NPP-bentonite,

Bentonite 21.75 20.20 3.33 x 10-2 0.951 22.72 7.55 x 10-2 0.996
NPP- 24.70 23.70 3.63 x 10-2 0.974 25.00 10.24 x 10-2 0.999
bentonite
Kaolinite 16.00 14.15 2.50 x 10-2 0.945 17.54 5.42 x 10-2 0.999
-2 -2
NPP- 19.00 17.80 3.00 x 10 0.982 20.00 6.94 x 10 0.994
kaolinite
4.5.4 Effect of initial Pb(II) concentration
The effect of initial Pb(II) concentration on adsorption of Pb(II) by bentonite,

NPP-bentonite, kaolinite and NPP-kaolinite is shown in Fig.4.43. It clearly illustrates
that increase in initial Pb(II) concentration from 10 mg/L to 50 mg/L in the solution
decreased the Pb(II) adsorption from 94.10 % to 87.00 %, 99.90 % to 98.80 %, 78.00
% to 64.00 % and 91.40 % to 76.00 %, respectively with increase in corresponding
Pb(II) adsorption capacity from 4.70 mg/g to 21.25 mg/g, 4.99 mg/g to 24.70 mg/g,
3.90 mg/g to 16.00 mg/g and 4.57 mg/g to 19.00 mg/g by bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite respectively.
Increase in initial metal ion concentration in the solution decreases the percent
adsorption which is due to the saturation of available adsorption sites on the clay but
decrease in adsorption capacity may be attributed to increased driving force of metal
ions towards active sites on the clay (Kumric et al., 2013).
126
100 30

80 Bentonite
20 NPP-bentonite
60
Kaolinite
NPP-kaolinite
40
10 Bentonite
20 NPP-bentonite
Kaolinite
0 0 NPP-kaolinite
0 20 40 60
Initial Pb(II) concentration (mg/L)
Fig.4.43 Effect of initial Pb(II) concentration on adsorption of Pb(II) by bentonite,

Figs.4.44 and 4.45 show the plots of Langmuir isotherm model and Freundlich
isotherm model. Table 4.23 summarizes the isotherm constants for Pb(II) adsorption
by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Results showed higher
Langmuir adsorption capacity (qm) of 35.71 mg/g for NPP-bentonite followed by
33.3 mg/g for bentonite, 26.31 mg/g for NPP-kaolinite and 23.80 mg/g for kaolinite.
This implies lesser adsorption sites on bentonite, NPP-kaolinite and kaolinite than on
NPP-bentonite.
Table 4.24 compares Langmuir adsorption capacity (qm) of various adsorbents for
Pb(II) adsorption. Separation factor (RL) values (0.0016 - 0.0025) suggest that Pb(II)
adsorption onto bentonite, NPP-bentonite, kaolinite and NPP-kaolinite was favorable.
Regression coefficient (R2) values were higher for Langmuir isotherm model for
Pb(II) adsorption by tested adsorbents. This confirmed that adsorption data fitted well
to Langmuir isotherm model.
Application to Freundlich isotherm model showed Kf value of 5.03

(mg/g)/(mg/L)1/n and n value of 0.95 which indicate higher adsorption capacity and
favorable adsorption. This shows better fitting of adsorption data to Freundlich
isotherm model for Pb(II) adsorption by NPP-bentonite alone but the model is not
127
applicable in case of Pb(II) adsorption by bentonite, kaolinite and NPP-kaolinite due to
lower regression coefficient (R2) values. This indicates that Pb(II) adsorption takes
place on both monolayer and multilayer only in case of NPP-bentonite but monolayer
pattern is applicable for bentonite, kaolinite and NPP-kaolinite.
2
Ce/qe (g/L)
Bentonite
1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0 20 40 60
Ce (mg/L)
Fig.4.44 Langmuir isotherm plots for adsorption of Pb(II) by bentonite, NPP-

2
log qe (mg/g)
1 Bentonite
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0.9 1.2 1.5 1.8
log Ce (mg/L)
Fig.4.45 Freundlich isotherm plots for adsorption of Pb(II) by bentonite, NPP-

128
Table 4.23 Isotherm constants for Pb(II) adsorption by bentonite, NPP-bentonite,

(mg/L)1/n
Bentonite 33.33 42.86 0.0023 0.992 4.48 0.95 0.947

NPP- 35.71 38.89 0.0025 0.999 5.03 0.95 0.998
bentonite
Kaolinite 23.80 61.80 0.0018 0.995 1.29 0.76 0.963
NPP- 26.31 52.70 0.0016 0.999 3.98 0.90 0.958
kaolinite
Table 4.24 Comparison of Pb(II) adsorption capacity by various adsorbents
Montmorillonite 31.10 Gupta and Bhattacharyya,

2008
Plum stones 21.20 Gala and Rydlewska, 2011
Granular bentonite 17.42 Nava et al., 2011
Nigerian natural clay 11.49 Njoku et al., 2011
Turkish illitic Clay 53.76 Ozdes et al., 2011
Bikougou clay 64.10 Eba et al., 2012
Ca-montmorillonite 13.65 Li et al., 2012 b
Portulaca oleracea leaves 192.30 Ackacha, 2013
Delonix regia pods 8.33 Festus et al., 2013
Kaolinite 10.41 Ghogomu et al., 2013
Thai bentonite 47.62 Ibrahim et al., 2013
Citrus nobilis peel 398.40 Inagaki et al., 2013
Smectite 9.35 Mhamdi et al., 2013
Walnut shell 2.94 Wolfov et al., 2013
129
Equation (4.10) and experimental results obtained were utilized in order to

develop central composite response surface model.
Adsorption (%) = 83.82 + 44.32 x A 2.48 x B + 2.85 x C + 1.61 x D 3.87 x A2

2.69 x B2 4.31 x C2 22.62 x D2 0.6 x AB + 0.467 x AC + 0.247 x AD + 0.778 x
BC + 0.412 x BD 0.32 x CD (4.10)
Pb(II) concentration (mg/L).
Experimental and predicted values for Pb(II) adsorption by NPP-bentonite are

compared in Table 4.25. The values clearly show that experimental values are closer
to predicted values. ANOVA for Pb(II) adsorption by NPP-bentonite is presented in
Table 4.26. The F-value of 43.51 at P-value 0.05 suggests the significance of the
model.
Fig.4.46 shows the 3D response surface plots of effects of pH, adsorbent dose,
contact time and initial Pb(II) concentration for adsorption of Pb(II) by NPP-
bentonite.
Pb(II) adsorption by NPP-bentonite was found to be 98.80 % (experimental) and

99.04 % (predicted). It was achieved under the following optimum conditions: pH 5.0,
adsorbent dose 2 g/L, contact time 60 min and initial Pb(II) concentration 50 mg/L.
This confirms the higher accuracy of the results obtained.
130
Table 4.25 Experimental and predicted values for Pb(II) adsorption by NPP-bentonite

A B C D
1 1 2 60 50 27.00 26.91
2 2 2 60 50 38.00 38.10
3 3 2 60 50 49.31 49.24
4 4 2 60 50 72.65 72.88
5 5 2 60 50 98.80 99.04
6 6 2 60 50 95.74 95.83
7 5 1 60 50 92.00 91.91
8 5 10 60 50 98.80 99.04
9 5 2 10 50 67.34 67.48
10 5 2 20 50 83.32 83.56
11 5 2 30 50 90.48 90.71
12 5 2 40 50 94.56 94.80
13 5 2 50 50 97.08 97.35
14 5 2 120 50 98.80 99.04
15 5 2 60 10 99.90 99.98
16 5 2 60 20 99.60 99.66
17 5 2 60 30 99.30 99.37
18 5 2 60 40 99.00 99.03
Table 4.26 ANOVA for Pb(II) adsorption by NPP-bentonite
Degree of
freedom
Model 8 10196.7 1274.587 43.5171 < 0.0001

Residual 21 7835.844 29.2892
Total 29 615.0748
A 1 10811.77 7835.844 267.5328 < 0.0001
B 1 25.9719 25.9719 0.8867 0.0357
C 1 51.3701 51.3701 1.7538 0.0199
D 1 614.5165 614.5165 20.9809 0.0002
A2 1 14.7051 14.7051 0.5020 0.4864
2
B 1 8.9226 8.9226 0.3046 0.5868
2
C 1 21.9485 21.9485 0.7493 0.3965
2
D 1 183.5883 183.5883 6.2681 0.0206
131
140.0
140.0
93.3
A d s o r p t io n ( % )
93.3
A d s o rp tio n (% )
46.7
46.7
0.0
0.0
6.0 6.0
4.3 1.0 4.3 10.0

4.0 46.7
pH 2.7 pH 2.7
7.0 83.3
1.0 10.0 Adsorbent dose (g/L) 1.0 120.0 Contact time (min)
140.0
100.0
93.3
80.0
46.7
60.0
0.0
40.0
6.0
120.0
4.3 10.0
10.0 83.3
pH 2.7
7.0
23.3
46.7 4.0
36.7 Contact time (min)
1.0 50.0 Adsorbent dose (g/L)
10.0 1.0
Pb(II) Concentration(mg/L)
100.0
100.0
80.0
80.0
60.0
60.0
40.0
40.0
10.0 120.0
50.0
50.0
7.0 36.7 83.3
36.7
4.0 23.3
Adsorbent dose (g/L) Pb(II) Concentration(mg/L) Contact time (min)
46.7 23.3
1.0 10.0 Pb(II) Concentration(mg/L)
10.0 10.0
and initial Pb(II) concentration for adsorption of Pb(II) by NPP-bentonite.
132
Results showed that at 30 min, NPP-bentonite showed maximum Pb(II)

desorption efficiency (95.34 %) followed by bentonite (81.32 %), NPP-kaolinite
(69.62 %) and kaolinite (56.34 %) for first cycle. But for third cycle, Pb(II) desorption
efficiency by NPP-bentonite, bentonite, NPP-kaolinite and kaolinite decreased to
71.28 %, 55.18 %, 42.84 % and 27.02 %, respectively (Fig.4.47).
Similarly, increasing the number of cycles from one to three decreased the Pb(II)
adsorption efficiency from 98.80 % to 80.18 % for regenerated NPP-bentonite,
87.00 % to 65.92 % for regenerated bentonite, 76.00 % to 52.14 % for regenerated
NPP-kaolinite and 64.00 % to 38.12 % for regenerated kaolinite. This decrease is
attributed to lesser number of adsorption sites available on the surface of adsorbents.
(a) Bentonite
100
50
Adsorption
Desorption
0
1 2 3
Number of cycles
(b) NPP-bentonite
100
50
Adsorption
Desorption
0
1 2 3
Number of cycles
133
(c) Kaolinite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
(d) NPP-kaolinite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
Fig.4.47 Pb(II) adsorption/desorption efficiency for (a) bentonite, (b) NPP-bentonite,

134
4.5.7 Adsorption of Pb(II) from fertilizer wastewater using bentonite, NPP-
Table 4.10 shows the Pb(II) concentration in fertilizer wastewater along with
other physico-chemical parameters. The Pb(II) concentration of fertilizer wastewater
was found to be 2.89 mg/L. Results showed higher Pb(II) adsorption from fertilizer
wastewater by bentonite (95.15 %), NPP-bentonite (99.65 %), kaolinite (79.23 %) and
NPP-kaolinite (92.38 %) under optimum conditions of pH 5.0, with 2 g/L adsorbent
dose and 60 min contact time. This clearly indicates affinity of Pb(II) towards all
tested adsorbents. Therefore, it can concluded that single cycle was enough to reduce
the Pb(II) concentration in fertilizer wastewater to below permissible limit before
discharging into the environment.
135
4.6 Adsorption of Malachite green by bentonite, NPP-bentonite, kaolinite and
NPP-kaolinite
4.6.1 Effect of pH
The pH of the dye solution is an important controlling parameter in the

adsorption because it affects the surface charge of the adsorbent, the degree of
ionization of the materials present in the solution, the structural stability, and the color
intensity of the dye molecule (Monash and Pugazhenthi, 2010).
Fig.4.48 shows the effect of pH an adsorption of Malachite green by bentonite,

NPP-bentonite, kaolinite and NPP-kaolinite. Increase in solution pH from 2.0 to 7.0
increased the Malachite green adsorption efficiency by tested adsorbents. At pH 2.0,
Malachite green adsorption by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
was found to be 52.40 %, 73.40 %, 31.90 %, and 41.80 %, respectively but thereafter
Malachite green adsorption efficiency increased to 82.10 % by bentonite, 94.90 % by
NPP-bentonite, 55.50 % by kaolinite and 68.70 % by NPP-kaolinite, with further
increasing the pH to 7.0. Results clearly show higher Malachite green adsorption
efficiency by NPP-bentonite and NPP-kaolinite than that of bentonite and kaolinite.
At lower pH, clay surface is covered with more number of H3O+ ions which get
replaced by OH- ions as the pH increases making the clay surface negatively charged
that will have preference for dye cations (Sarma et al., 2011).
Similar trends have been reported for adsorption of Malachite green by kaolin
(Bagha et al., 2011), HDTMA-modified montmorillonite (Cardenas et al., 2013),
Al-Hussainiyat clay (Dhahir et al., 2013), and solgel-bentonite nanocomposite
(Mahdinloo and Nouri, 2013).
136
Malachite green adsorption (%)
100
80
60 Bentonite
40 NPP-bentonite
Kaolinite
20 NPP-kaolinite
0
0 2 4 6 8
pH
Fig.4.48 Effect of pH on adsorption of Malachite green by bentonite, NPP-bentonite,

The effect of dose of adsorbents such as bentonite, NPP-bentonite, kaolinite and

NPP-kaolinite on adsorption of Malachite green is depicted in Fig.4.49. It clearly
illustrates that Malachite green adsorption efficiency increased from 68.20 % to 82.10
%, 87.10 % to 94.90 %, 43.20 % to 55.50 % and 51.60 % to 68.70 %, respectively by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite with increase in dose of
adsorbents from 0.5 g/L to 1.0 g/L. On other hand, Malachite green adsorption
capacity decreased from 68.20 mg/g to 41.05 mg/g for bentonite, 87.10 mg/g to 47.45
mg/g for NPP-bentonite, 43.20 mg/g to 27.75 mg/g for kaolinite and 51.60 mg/g to
34.35 mg/g for NPP-kaolinite with increase in dose of adsorbents from 0.5 g/L to 1.0
g/L. Higher Malachite green adsorption efficiency and adsorption capacity by NPP-
bentonite and NPP-kaolinite than other tested adsorbents is due to their larger SSA
and CEC.
Increase in adsorption efficiency of adsorbents is due to increased availability of

surface active sites (Al-Jobouri et al., 2013). Decrease in adsorption capacity is
attributed to the fact that a large amount of adsorbent reduces the unsaturation of the
adsorption sites and correspondingly, the number of such sites per unit mass comes
down resulting in comparatively less adsorption at higher adsorbent amount, and
137
higher amount of adsorbent creates particle aggregation resulting in decrease in total
surface of adsorbent (Sarma et al., 2011).
100 100

80 80 Bentonite
NPP-bentonite
60 60
Kaolinite
NPP-kaolinite
40 40
Bentonite
20 20 NPP-bentonite
Kaolinite
0 0 NPP-kaolinite
0 1 2 3 4 5
Fig.4.49 Effect of dose of adsorbents on adsorption of Malachite green by bentonite,

The effect of contact time on adsorption of Malachite green by bentonite, NPP-

bentonite, kaolinite and NPP-kaolinite is illustrated in Fig.4.50. It can be observed
that Malachite green adsorption took place rapidly within 30 min by bentonite (75.94
%), NPP-bentonite (87.96 %), kaolinite (49.66 %) and NPP-kaolinite (62.42 %).
Equilibrium was reached at 60 min with maximum Malachite green adsorption of
82.10 % for bentonite, 94.90 % for NPP-bentonite, 55.50 % for kaolinite and 68.70 %
for NPP-kaolinite. This may be attributed to the fact that, at initial stage more number
of vacant adsorption sites are available on adsorbent surface which get occupied at
later stages by Malachite green molecules as a result the number of vacant adsorption
sites decrease.
138
100

80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 50 100 150
Contact time (min)
Fig.4.50 Effect of contact time on adsorption of Malachite green by bentonite, NPP-

Plots of pseudo-first order model and pseudo-second order model are shown in
Figs.4.51 and 4.52. The kinetic parameters for Malachite green adsorption by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are listed in Table 4.27.
Results show that pseudo-first order rate constants (K1) for Malachite green
adsorption by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite varied from
3.63 x 10-2 to 6.00 x 10-2 g/mg min but qe cal values obtained largely differed than that
of qe exp values which indicate the non applicability of pseudo-first order model.
Higher pseudo-second order rate constant (K2) of 14.81 x 10-2 is achieved by

NPP-bentonite followed by 11.18 x 10-2 for bentonite, 9.42 x 10-2 for NPP-kaolinite
and 7.63 x 10-2 for kaolinite, which show rapid Malachite green adsorption by tested
adsorbents. The qe cal values of pseudo-second order model are closer to qe exp values
2
and higher regression coefficient (R ) values obtained reveal better fitting of
equilibrium data to pseudo-second order model. This confirms the involvement of
chemical adsorption through exchange or sharing of electrons between adsorbate and
adsorbent (Zehhaf et al., 2012).
139
1.5

1
Bentonite
0.5 NPP-bentonite
Kaolinite
NPP-kaolinite
0
0 20 40 60
-0.5
Time (min)
Fig.4.51 Pseudo-first order plots for adsorption of Malachite green by bentonite, NPP-
3
t/qt (min g/mg)
2
Bentonite
NPP-bentonite
1 Kaolinite
NPP-kaolinite
0
0 20 40 60 80
Time (min)
Fig.4.52 Pseudo-second order plots for adsorption of Malachite green by bentonite,

140
Table 4.27 Kinetic parameters for Malachite green adsorption by bentonite, NPP-

Bentonite 41.05 12.00 5.00 x 10-2 0.975 43.47 11.87 x 10-2 0.996
-2 -2
NPP- 47.45 13.55 6.00 x 10 0.986 47.61 14.81 x 10 0.999
bentonite
Kaolinite 27.75 10.30 3.63 x 10-2 0.954 27.77 7.63 x 10-2 0.999
NPP- 34.35 11.60 4.28 x 10-2 0.967 35.71 9.42 x 10-2 0.994
kaolinite
4.6.4 Effect of initial Malachite green concentration
Fig.4.53 shows the effect of initial Malachite green concentration on adsorption

by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Results show that
Malachite green adsorption capacity increases from 9.23 mg/g to 41.05 mg/g for
bentonite, 9.98 mg/g to 47.45 mg/g for NPP-bentonite, 7.21 mg/g to 27.75 mg/g for
kaolinite and 8.00 mg/g to 34.35 mg/g for NPP-kaolinite with increase in initial
Malachite green concentration from 10 mg/L to 50 mg/L. The percent Malachite
green adsorption decreases from 92.30 % to 82.10 % for bentonite, 99.80 % to 94.90
% for NPP-bentonite, 72.10 % to 55.50 % for kaolinite and 80.00 % to 68.70 % for
NPP-kaolinite when the initial Malachite green concentration increased from 10 mg/L
to 50 mg/L.
With increase in initial adsorbate concentration, the driving force of adsorbate

towards the active adsorption sites on the adsorbent increases as a result the
adsorption increases. On other hand, decrease in percent adsorption may be due to the
saturation of available active adsorption sites on the adsorbent surface (Jiang et al.,
2010; Ozdes et al., 2011).
141
100 50

Bentonite
80 40
NPP-bentonite
60 30 Kaolinite
NPP-kaolinite
40 20
Bentonite
NPP-bentonite
20 10
NPP-bentonite
0 0 NPP-kaolinite
0 20 40 60
Initial Malachite green concentration (mg/L)
Fig.4.53 Effect of initial Malachite green concentration on adsorption of Malachite

green by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite.
Langmuir and Freundlich isotherms plots are shown in Figs.4.54 and 4.55. The
isotherm constants for Malachite green adsorption by tested adsorbents are presented
in Table 4.28. Results show higher Langmuir adsorption capacity (qm) by NPP-
bentonite (62.50 mg/g) and NPP-kaolinite (45.45 mg/g) as compared to that of
bentonite (55.55 mg/g) and kaolinite (35.71 mg/g). This suggests the presence of
larger number of adsorption sites on NPP-bentonite and NPP-kaolinite than that of
bentonite and kaolinite.
Langmuir adsorption capacity (qm) of various adsorbents for Malachite green

adsorption are tabulated in Table 4.29. The adsorption data fitted well to Langmuir
isotherm model which is confirmed by separation factor (RL) values (< 1) and higher
regression coefficient (R2) values. Freundlich isotherm model is not applicable due to
lower regression coefficient (R2) values than those obtained with Langmuir isotherm
model. It can be concluded that Malachite green adsorption by bentonite, NPP-
bentonite, kaolinite and NPP-kaolinite takes place on monolayer.
142
2

1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0 20 40 60
Ce (mg/L)
Fig.4.54 Langmuir isotherm plots for adsorption of Malachite green by bentonite,

2
log qe (mg/g)
1 Bentonite
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0.9 1.2 1.5 1.8
log Ce (mg/L)
Fig.4.55 Freundlich isotherm plots for adsorption of Malachite green by bentonite,

143
Table 4.28 Isotherm constants for Malachite green adsorption by bentonite, NPP-

(mg/L)1/n
Bentonite 55.55 25.00 0.0039 0.999 5.01 0.90 0.910

NPP- 62.50 26.68 0.0037 0.999 5.51 0.95 0.981
bentonite
Kaolinite 35.71 22.46 0.0028 0.999 3.11 0.71 0.924
NPP- 45.45 34.49 0.0044 0.997 3.98 0.90 0.930
kaolinite
Table 4.29 Comparison of Malachite green adsorption capacity by various adsorbents
Rattan sawdust 62.71 Hameed and El-Khaiary,

2008
Ginger Waste 84.03 Ahmad and Kumar, 2010
Degreased coffee bean 55.30 Baek et al., 2010
Hydrilla verticillata 69.88 Kannan et al., 2011
Morroccan clay 53.78 Karim et al., 2011
Acid-activated kapok hull 43.60 Syed, 2011
EDTA-modified groundnut husk 46.78 Titilayo et al., 2012
Dates seeds 158.98 Al-Ahmary, 2013
HDTMA-modified montmorillonite 56.82 Cardenas et al., 2013
Al-Hussainiyat clay 0.81 Dhahir et al., 2013
Stishovite clay 8.22 Venkateswaran et al., 2013
Pyrolytic char 91.24 Zou et al., 2013
144
Results show Malachite green desorption efficiency by tested adsorbents in the

following order: 92.90 % (NPP-bentonite) > 78.14 % (bentonite) > 63.68 % (NPP-
kaolinite) > 49.52 % (kaolinite). These have been achieved with 15 min contact time
(Figs.4.56 a, b, c and d). As the number of cycles increased from one to three,
Malachite green adsorption efficiency by regenerated bentonite, regenerated NPP-
bentonite, regenerated kaolinite and regenerated NPP-kaolinite decreased from 82.10
% to 73.04 %, 94.90 % to 87.84 %, 55.50 % to 42.62 % and 68.70 % to 57.66 %,
respectively. This is due to the decrease in number of adsorption sites on the surface
of adsorbents.
(a) Bentonite
100
50
Adsorption
Desorption
0
1 2 3
Number of cycles
(b) NPP-bentonite
Adsoprtion/desorption (%)
100
50
Adsorption
Desorption
0
1 2 3
Number of cycles
145
(c) Kaolinite
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
(d) NPP-kaolinite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
Fig.4.56 Malachite green adsorption/desorption efficiency for (a) bentonite, (b) NPP-
bentonite, (c) kaolinite and (d) NPP-kaolinite.
146
4.6.6 Adsorption of Malachite green from textile wastewater using bentonite
NPP-bentonite, kaolinite and NPP-kaolinite
The physico-chemical characteristics of textile wastewater are summarized in

Table 4.30. At pH 7.0, with 1 g/L adsorbent dose and 60 min contact time, maximum
Malachite green adsorption from textile wastewater by bentonite, NPP-bentonite,
kaolinite and NPP-kaolinite was found to be 81.76 %, 95.14 %, 53.28 % and 67.05 %
respectively. This indicates the effectiveness of tested adsorbents in adsorbing
Malachite green from textile wastewater.
Table 4.30 Physico-chemical characteristics of textile wastewater
Parameters Content
Color Greenish blue

pH 8.64
Dissolved oxygen (mg/L) Nil
Chemical oxygen demand (mg/L) 719
147
4.7 Adsorption of Victoria blue B by bentonite, NPP-bentonite, kaolinite and
NPP-kaolinite
4.7.1 Effect of pH
The pH value of the solution, which affects the surface charge of the adsorbent
and the degree of speciation of adsorbate, is an important controlling parameter in the
adsorption process (Li et al., 2010). The effect of pH on adsorption of Victoria blue B
by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite is depicted in Fig.4.57.
Victoria blue B adsorption efficiency by tested adsorbents increased with an

increase in pH of the solution. As the pH increased from 2.0 to 7.0, Victoria blue B
adsorption efficiency by bentonite, NPP-bentonite, kaolinite, NPP-kaolinite also
45.93 % to 74.10 %, respectively. This indicates that Victoria blue B adsorption onto
bentonite and kaolinite is 13 % to 14 % lesser than that of NPP-bentonite and NPP-
kaolinite.
At lower pH, clay surface is covered with more number of H3O+ ions which get
replaced by OH- ions as the pH increases making the clay surface negatively charged
that will have preference for dye cations (Sarma et al., 2011). Similar trends have
been reported for Victoria blue B adsorption by China clay (Singh and Singh, 2006),
and bentonite (Sundaram et al., 2011).
Victoria blue B adsorption (%)
100
80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 2 4 6 8
pH
Fig.4.57 Effect of pH on adsorption of Victoria blue B by bentonite, NPP-bentonite,

148
Fig.4.58 depict the effect of dose of adsorbents on adsorption of Victoria blue B

by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Results illustrate that
increase in dose of adsorbents from 0.5 g/L to 1.0 g/L decreased the Victoria blue B
adsorption capacity from 75.80 mg/g to 42.55 mg/g by bentonite, 91.20 mg/g to 49.25
mg/g by NPP-bentonite, 47.10 mg/g to 30.15 mg/g by kaolinite and 56.40 mg/g to
37.05 mg/g by NPP-kaolinite but corresponding adsorption efficiency increased from
75.80 % to 85.10 %, 91.20 % to 98.50 %, 47.10 % to 60.30 % and 56.40 % to 74.10
% respectively by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. This shows
that Victoria blue B adsorption capacity and adsorption efficiency by NPP-bentonite
and NPP-kaolinite are higher than that of bentonite and kaolinite due to higher SSA
and CEC of NPP-bentonite and NPP-kaolinite.
Decrease in adsorption capacity is attributed to (Sarma et al., 2011):
A large amount of adsorbent reduces the unsaturation of the adsorption sites

and correspondingly, the number of such sites per unit mass comes down
resulting in comparatively less adsorption at higher adsorbent amount, and
Higher amount of adsorbent creates particle aggregation, resulting in decrease

in total surface of adsorbent.
However, increase in adsorption efficiency may be attributed to increased adsorbent

surface area and availability of more adsorption sites (Tahir et al., 2013).
149
100 100

80 80 Bentonite
NPP-bentonite
60 60
Kaolinite
NPP-kaolinite
40 40
Bentonite
20 20 NPP-bentonite
Kaolinite
0 0
NPP-kaolinite
0 1 2 3 4 5
Fig.4.58 Effect of dose of adsorbents on adsorption of Victoria blue B by bentonite,

The effect of contact time on adsorption of Victoria blue B by bentonite, NPP-

bentonite, kaolinite and NPP-kaolinite is shown in Fig.4.59. Results show that
Victoria blue B interaction with tested adsorbents was rapid in first 30 min with
adsorption efficiency of 79.68 % for bentonite, 91.18 % for NPP-bentonite, 56.92 %
for kaolinite and 69.44 % for NPP-kaolinite. Thereafter, interaction was slow and
equilibrium was reached at 60 min. At 60 min, maximum Victoria blue B adsorption
efficiency by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite was found to be
85.10 %, 98.50 %, 60.30 % and 74.10 %, respectively. This may be attributed to large
number of vacant adsorption sites which are available for Victoria blue B adsorption
during initial stages, but these get occupied by Victoria blue B molecules at later
stages and this in turn decrease the number of vacant adsorption sites.
150
100

80
60 Bentonite
NPP-bentonite
40
Kaolinite
20 NPP-kaolinite
0
0 50 100 150
Contact time (min)
Fig.4.59 Effect of contact time on adsorption of Victoria blue B by bentonite, NPP-

Pseudo-first order and pseudo-second order plots are depicted in Figs.4.60 and
4.61. Table 4.31 summarizes the kinetic parameters for Victoria blue B adsorption by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite.
It is clear that pseudo-first order model is not applicable for Victoria blue B
adsorption by tested adsorbents due to large deviation of qe cal values from that of
qe exp values. Pseudo-second order rate constants (K2) for NPP-bentonite (20.61 x 10-2
g/mg min) and NPP-kaolinite (12.15 x 10-2 g/mg min) were found to be higher than
that of bentonite (18.41 x 10-2 g/mg min) and kaolinite (10.01 x 10-2 g/mg min). This
indicates faster Victoria blue B adsorption by NPP-bentonite and NPP-kaolinite. The
qe cal values obtained from pseudo-second order model are closer to qe exp values and
higher regression coefficient (R2) values suggest that equilibrium data fitted well to
pseudo-second order model. This confirms the involvement of chemical adsorption
process through exchange or sharing of electrons between adsorbate and adsorbent
(Zehhaf et al., 2012).
151
2
1.5

1
Bentonite
0.5 NPP-bentonite
Kaolinite
0 NPP-kaolinite
0 20 40 60
-0.5
-1
Time (min)
Fig.4.60 Pseudo-first order plots for adsorption of Victoria blue B by bentonite, NPP-
3
t/qt (min g/mg)
2
Bentonite
NPP-bentonite
1
Kaolinite
NPP-kaolinite
0
0 20 40 60 80
Time (min)
Fig.4.61 Pseudo-second order plots for adsorption of Victoria blue B by bentonite,

152
Table 4.31 Kinetic parameters for Victoria blue B adsorption by bentonite, NPP-

Bentonite 42.55 11.00 5.71 x 10-2 0.919 43.47 18.41 x 10-2 0.999
NPP- 49.25 14.35 7.14 x 10-2 0.953 50.00 20.61 x 10-2 0.999
bentonite
Kaolinite 30.15 7.05 4.16 x 10-2 0.938 30.30 10.01 x 10-2 0.999
-2 -2
NPP- 37.05 9.50 5.00 x 10 0.949 38.46 12.15 x 10 0.999
kaolinite
4.7.4 Effect of initial Victoria blue B concentration
Results show that increase in initial Victoria blue B concentration in solution

from 10 mg/L to 50 mg/L increased Victoria blue B adsorption capacity from 9.52
mg/g to 42.55 mg/g, 9.99 mg/g to 49.25 mg/g, 7.60 mg/g to 30.15 mg/g and 8.43
mg/g to 37.05 mg/g with decrease in corresponding percentage Victoria blue B
adsorption from 95.20 % to 85.10 %, 99.90 % to 98.50 %, 76.00 % to 60.30 % and
84.30 % to 47.10 %, respectively by bentonite, NPP-bentonite, kaolinite and NPP-
kaolinite (Fig.4.62).
At higher adsorbate concentration, increase in adsorption capacity was observed

which may be attributed to increased driving force of adsorbate towards active sites
present on the clay. Though increase in adsorption capacity was observed, decrease in
percent adsorption was due to saturation of adsorption sites on the clay (Kumric et al.,
2013).
153
100 60

80 50
Bentonite
40 NPP-bentonite
60
30 Kaolinite
40 NPP-kaolinite
20
Bentonite
20 10 NPP-bentonite
Kaolinite
0 0
NPP-kaolinite
0 20 40 60
Initial Victoria blue B concentration (mg/L)
Fig.4.62 Effect of initial Victoria blue B concentration on adsorption of Victoria blue

B by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite.
Figs.4.63 and 4.64 show the plots of Langmuir isotherm model and Freundlich
isotherm model. Table 4.32 presents isotherm constants for Victoria blue B adsorption
by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite.
Results show that Langmuir adsorption capacity (qm) varied from 38.46 mg/g to
66.66 mg/g for bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Affinity of
Victoria blue B molecules towards tested adsorbents was in the following order: NPP-
bentonite > bentonite > NPP-kaolinite > kaolinite. This indicates the presence of
larger number of adsorption sites on NPP-bentonite than that of bentonite, NPP-
kaolinite and kaolinite. Comparison of Langmuir adsorption capacity (qm) of various
adsorbents for Victoria blue B adsorption is presented in Table 4.33. Separation factor
(RL) values (< 1) and higher regression (R2) coefficient values suggest that Victoria
blue B adsorption on bentonite, NPP-bentonite, kaolinite and NPP-kaolinite showed
good representation with Langmuir isotherm model than that of Freundlich isotherm
model. This confirms that Victoria blue B adsorption by tested adsorbents takes place
on monolayer.
154
2

1
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0 20 40 60
Ce (mg/L)
Fig.4.63 Langmuir isotherm plots for adsorption of Victoria blue B by bentonite,

2
log qe (mg/g)
1 Bentonite
NPP-bentonite
Kaolinite
NPP-kaolinite
0
0.9 1.2 1.5 1.8
log Ce (mg/L)
Fig.4.64 Freundlich isotherm plots for adsorption of Victoria blue B by bentonite,

155
Table 4.32 Isotherm constants for Victoria blue B adsorption by bentonite, NPP-

(mg/L)1/n
Bentonite 58.82 23.29 0.0042 0.999 5.51 0.95 0.921

NPP- 66.66 20.00 0.0049 0.997 6.33 0.95 0.907
bentonite
Kaolinite 38.46 27.66 0.0043 0.999 3.28 0.83 0.930
NPP- 47.61 23.60 0.0042 0.998 4.28 0.90 0.946
kaolinite
Table 4.33 Comparison of Victoria blue B adsorption capacity by various adsorbents
Perlite 3.68 Demirbas et al., 2002

Bentonite 5.36 Sundaram et al., 2011
Activated carbon/Ba/alginate 3.21 Kumar et al., 2013
beads
Central composite response surface model was developed using experimental

results and equation (4.11).
Adsorption (%) = 76.04 0.34 x A + 4.52 x B 1.67 x C 12.8 x D 0.21 x A2

4.70 x B2 8.75 x C2 14.43 x D2 1.0 x AB + 0.778 x AC + 0.090 x AD + 0.778 x
BC + 0.090 x BD 0.07 x CD (4.11)
Victoria blue B concentration (mg/L).
156
Table 4.34 presents the comparison of experimental and predicted values for
Victoria blue B adsorption by NPP-kaolinite. It is clear that predicted values are
closer to experimental values. Table 4.35 summarizes ANOVA for Victoria blue B
adsorption by NPP-kaolinite. The F-value of 32.04 at P-value 0.05 clearly
demonstrates that the model of the present study is significant.
Fig.4.65 shows the 3D response surface plots of effects of pH, adsorbent dose,
contact time and initial Victoria blue B concentration for adsorption of Victoria blue
B by NPP-kaolinite.
At pH 7.0, with 1g/L adsorbent dose, 60 min contact time and 50 mg/L initial
Victoria blue B concentration, maximum Victoria blue B adsorption efficiency of
74.92 % (predicted) and 74.10 % (experimental) was achieved. This proves the
accuracy of the results obtained under optimized conditions.
Table 4.34 Comparison of experimental and predicted values for Victoria blue B
adsorption by NPP-kaolinite

A B C D
1 2 1 60 50 45.93 45.81
2 3 1 60 50 53.95 53.90
3 4 1 60 50 61.00 61.22
4 5 1 60 50 67.21 67.58
5 6 1 60 50 71.65 71.96
6 7 1 60 50 74.10 74.92
7 7 0.5 60 50 56.40 56.69
8 7 1.5 60 50 74.10 74.92
9 7 1 10 50 55.10 55.24
10 7 1 20 50 65.24 65.33
11 7 1 30 50 69.44 69.59
12 7 1 40 50 71.68 71.78
13 7 1 50 50 73.08 73.41
14 7 1 120 50 74.10 74.92
15 7 1 60 10 84.30 84.92
16 7 1 60 20 81.55 81.81
17 7 1 60 30 78.90 79.09
18 7 1 60 40 76.45 76.53
157
Table 4.35 ANOVA for Victoria blue B adsorption by NPP-kaolinite
Degree of
freedom
Model 8 2974.797 371.8496 32.0469 < 0.0001

Residual 22 255.2725 11.6032
Total 30 3230.069
A 1 1533.001 1533.001 132.1178 < 0.0001
B 1 168.9472 168.9472 14.5602 0.0009
C 1 17.1526 17.1526 1.4782 0.0236
D 1 216.8865 216.8865 18.6918 0.0003
A2 1 105.1917 105.1917 9.0656 0.0064
B2 1 3.0889 3.0889 0.2662 0.6110
C2 1 49.9199 49.9199 4.3022 0.0500
D2 1 46.7962 46.7962 4.0330 0.0571
158
and initial Victoria blue B concentration for adsorption of Victoria blue B by NPP-
kaolinite.
159
Figs.4.66 a, b, c and d show Victoria blue B adsorption/desorption efficiencies

for bentonite, NPP-bentonite, kaolinite and NPP-kaolinite. Results show that at
15 min with increase in number of cycles from one to three, Victoria blue B
desorption efficiency by bentonite, NPP-bentonite, kaolinite and NPP-kaolinite
decreased from 82.10 % to 72.00 %, 97.52 % to 89.38 %, 55.32 % to 41.20 % and
70.06 % to 58.12 % respectively. In third cycle, Victoria blue B adsorption efficiency
by regenerated bentonite (78.06 %) and regenerated kaolinite (49.32 %) was lower
than that of regenerated NPP-bentonite (93.48 %) and regenerated NPP-kaolinite
(65.18 %). This could be attributed to decrease in number of adsorption sites on the
surface of adsorbents.
(a) Bentonite
100
50
Adsorption
Desorption
0
1 2 3
Number of cycles
(b) NPP-bentonite
100
50
Adsorption
Desorption
0
1 2 3
Number of cycles
160
(c) Kaolinite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
(d) NPP-kaolinite
80
60
40
Adsorption
20 Desorption
0
1 2 3
Number of cycles
Fig.4.66 Victoria blue B adsorption/desorption efficiency for (a) bentonite, (b) NPP-
bentonite, (c) kaolinite and (d) NPP-kaolinite.
4.7.7 Adsorption of Victoria blue B from textile wastewater using bentonite NPP-
The physico-chemical characteristics of textile wastewater are similar to that

presented in Table 4.30. Victoria blue B adsorption from textile wastewater by
bentonite, NPP-bentonite, kaolinite and NPP-kaolinite was 89.60 %, 99.12 %,
66.83 % and 78.54 %, respectively. The optimum conditions were pH 7.0, adsorbent
dose of 1 g/L and contact time of 60 min. This reveals higher decolorization of
Victoria blue B from textile wastewater by NPP-bentonite, bentonite and NPP-
kaolinite. But in case of kaolinite slight presence of color was observed which was
removed by the application of second cycle.
161

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CHAPTER-IV

RESULTS AND DISCUSSION

4.1.1 XRD study

XRD patterns of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are

XRD pattern of NPP-bentonite revealed the disappearance of quartz peaks (2 =

XRD patterns of both NPP-bentonite and NPP-kaolinite showed almost same

Fig.4.1 XRD patterns of bentonite and NPP-bentonite.

Fig.4.2 XRD patterns of kaolinite and NPP-kaolinite.

K+Q (1.66 ) K+Q (1.66 )

Chemical composition of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite

Table 4.1 Chemical composition of bentonite, NPP-bentonite, kaolinite and NPP-

Constituents Weight (%)

Bentonite NPP-bentonite Kaolinite NPP-kaolinite

4.1.3 FTIR study

FTIR spectra of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are shown

Band position (cm-1) Band assignment

Band position (cm-1) Band assignment

The SEM images of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are

(a) Bentonite (b) NPP-bentonite

(c) Kaolinite (d) NPP-kaolinite

SSA and CEC of bentonite, NPP-bentonite, kaolinite and NPP-kaolinite are

Adsorbent SSA (m2/g) CEC (meq/100 g)

Bentonite 39.00 67.37

4.1.6 Reaction mechanism of bentonite and kaolinite modification with sodium

Fig.4.6 Reaction mechanism of modification of bentonite with sodium pyrophosphate

Fig.4.7 Reaction mechanism of modification of kaolinite with sodium pyrophosphate

As(III) adsorption from aqueous solutions increased with increase in pH of the

At low pH of solution, As(III) exists in the form of H3 AsO3, which shifts to

X OH + H3AsO3 X HAsO3 + H2O (monodentate) (4.1)

2X OH + H3AsO3 X2 HAsO3 + 2H2O (bidentate) (4.2)

At near neutral pH values (7 - 9) slow dissociation of H3 AsO3 producing Arsenite

Fig.4.8 Effect of pH on adsorption of As(III) by bentonite, NPP-bentonite, kaolinite

4.2.2 Effect of adsorbent dose

Fig.4.9 shows the effect of dose of adsorbents on adsorption of As(III) by

Increase in adsorption efficiency is attributed to the increase in surface area

Presence of large amount of adsorbent reduces the unsaturation of the

Higher amount of adsorbent creates particle aggregation resulting in decrease

Adsorption capacity (mg/g)

Fig.4.9 Effect of dose of adsorbents on adsorption of As(III) by bentonite, NPP-

4.2.3 Effect of contact time

Effect of contact time on adsorption of As(III) by bentonite, NPP-bentonite,

As(III) adsorption (%)

Fig.4.10 Effect of contact time on adsorption of As(III) by bentonite, NPP-bentonite,

4.2.3.1 Adsorption kinetics

Fig.4.11 Pseudo-first order plots for adsorption of As(III) by bentonite, NPP-

Fig.4.12 Pseudo-second order plots for adsorption of As(III) by bentonite, NPP-

Adsorbent Pseudo-first order model Pseudo-second order model

qe exp qe cal K1 (l/min) R2 qe cal K2 (g/mg R2

4.2.4 Effect of initial As(III) concentration

The results showed that As(III) adsorption capacity by bentonite, NPP-bentonite,

Adsorption capacity (mg/g)

Fig.4.13 Effect of initial As(III) concentration on adsorption of As(III) by bentonite,

4.2.4.1 Adsorption isotherms

The Langmuir adsorption capacity (qm) for As(III) adsorption by tested

Ce/qe (g/L) Bentonite

Fig.4.14 Langmuir isotherm plots for adsorption of As(III) by bentonite, NPP-

Fig.4.15 Freundlich isotherm plots for adsorption of As(III) by bentonite, NPP-

Adsorbent Langmuir Isotherm Freundlich Isotherm

qm (mg/g) b (L/g) RL R2 Kf (mg/g)/ n R2

Bentonite 15.15 150.15 0.0006 0.998 1.18 0.62 0.936

Table 4.7 Comparison of As(III) adsorption capacity by various adsorbents

Adsorbent qm (mg/g) Reference

HDTMA-modified kaolinite 0.32 Li et al., 2007