Journal of Molecular Liquids 299 (2020) 112261

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Journal of Molecular Liquids

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

Process modeling and optimization of an iron oxide immobilized

graphene oxide gadolinium nanocomposite for arsenic adsorption
Lakshmi Prasanna Lingamdinne a, Jong-Soo Choi a, Yu-Lim Choi a, Yoon-Young Chang a, Jae-Kyu Yang a,
Rama Rao Karri b,⁎, Janardhan Reddy Koduru a,⁎
a
Department of Environmental Engineering, Kwangwoon University, Seoul 01897, Republic of Korea
b
Petroleum and Chemical Engineering, Faculty of Engineering, Universiti Teknologi Brunei, Brunei Darussalam

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

Article history: In this study, a novel nanosized iron-oxide-immobilized graphene oxide–gadolinium oxide (Fe-GO-Gd) adsor-
Received 9 August 2019 bent was synthesized and applied for adsorption removal of As(V). The purity, chemical composition, and crys-
Received in revised form 3 December 2019 talline size of Fe-GO-Gd was investigated using microscopic and spectroscopic studies. The results found that the
Accepted 4 December 2019
mesoporous crystalline nanoparticles were 40 nm with active surface functional groups (–C=O, –C–C=C–, OH–
Available online 6 December 2019
C=O, Fe2+ and Fe3+, and Gd2O3). The adsorption process was optimized using response surface methodology
Keywords:
with a central composite design framework. The synthesized nanocomposite showed significant arsenic adsorp-
Arsenic removal tion removal. The study of the interaction effects showed that adsorption removal efficacy is directly proportional
Batch adsorption to the adsorbent dosage, pH, and residence time, whereas it is inversely proportional to the initial concentration.
Iron oxide immobilized graphene oxide The curvature nature of the contour plots confirmed the interaction intensity among the independent process
Gadolinium oxide variables. The As(V) removal (%) enhanced from 16.3 to 98.0% as the dosage increased from 0.1 to 1.0 g/L. The
Nanocomposite quadratic model identified from analysis of variance, has resulted in model predictions that has R2 = 0.889, in-
Response surface methodology dicating the model efficiency. Based on the RSM model, the highest As(V) removal efficiency of 94.8% can be
achieved at the optimal conditions of Initial concentrations, adsorbent dosage, pH and residence time of
25.0 mg/L, 0.70 g/L, 4.0 and 187 min respectively. The Fe-GO-Gd nanocomposite showed good stability without
loss of adsorption capacity up to 3 cycles and hence can be a potential candidate for sustainable water
purification.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction The increasing of toxic pollutants in aquatic water bodies and

The growth of industrialization and human needs has driven new
manufacturing industries which in turn generating enormous waste
and toxic effluents. These generating pollutants are released into
water bodies, thus polluting the environment. Among these pollutants,
arsenic is a carcinogenic element which has lethal health effects on
human beings such as bone marrow disorder, cardiovascular diseases,
gastrointestinal diseases, and kidney cancer [1–3]. The primary sources
of arsenic release into aquatic bodies are from mining-related indus-
tries, agricultural pesticides, human-made arsenic compound leaching,
natural weathering processes, and many other anthropogenic activities
[1]. Arsenic usually shows multiple oxidations states (−3, 0, +3, and
+5); among these As(III) and As(V) are the most commonly occurring
in water bodies. The maximum permissible limits for arsenic in water
bodies is approximately 0.01 mg/L [4].
⁎ Corresponding authors.
E-mail addresses: kramarao.iitd@gmail.com (R.R. Karri), reddyjchem@gmail.com
(J.R. Koduru).
groundwater has driven researchers to explore techniques that are
less expensive and more efficient. Among various techniques used for
water treatment, adsorption has found to be more feasible technique
because of its features of low cost, easy use, and less investment [5–7].
However, the efficiency of this process depends on the characteristics
of the adsorbent used. In this regard, researchers have tried different ad-
sorbents based on iron oxides and hydroxides, chemically activated
granular activated carbon, copper oxide impregnated alumina, zero-
valent iron, and magnetic oxide [8–13]. Moreover, iron oxide-based
nanomaterials are very active in the adsorption removal of As(III) and
As(V). However, the application of these adsorbents in the field is diffi-
cult because of their small particle size and instability when exposed to
the atmosphere. To avoid the aforementioned issues, iron oxides have
been immobilized with other compounds. Many researchers have con-
ducted experiments using iron oxides immobilized with graphene or
graphene oxide (GO) [3,14–17].
Based on a literature survey, one potential means to intensify
the adsorption of anionic arsenic species onto GO is inorganic
loading on the GO surface for the adsorptive removal of anions

https://doi.org/10.1016/j.molliq.2019.112261
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261
from water [16,18,19]. However, gadolinium oxonium ions pos-
sess a sizeable magnetic moment along with great interactions to-
wards nitrogen, carbon, sulfur, phosphorus, boron, selenium,
silicon, and arsenic at elevated temperatures, forming binary
compounds [18]. Moreover, to the best of our knowledge, applica-
tion of gadolinium based nanocomposites for wastewater treat-
ment have not yet been reported in the open literature thus far.
Here, to enhance iron immobilized GO stability and rapid mag-
netic separation with high adsorption efficiency for arsenic, gado-
linium oxide was chosen as a surfactant for the preparation of
iron immobilized-GO-gadolinium oxide. In addition, gadolinium
oxide is promising as a host matrix because of its excellent chem-
ical durability, low photon energy, and similar properties to those
of Fe(III) and Al(III) [19].
In this research study, a novel nanocomposite-material-based
iron oxide immobilized graphene oxide-gadolinium (Fe-GO-Gd)
was synthesized and investigated for arsenic removal from aque-
ous media. To understand the inherent adsorption mechanisms
and evaluate the performance of arsenic removal using Fe-GO-
Gd as an adsorbent, a systematic experimental procedure was
followed. The interaction effects of various process parameters
on arsenic removal efficiency were ergonomically evaluated
using the response surface methodology (RSM). The dependency
of arsenic removal efficiency on four independent process vari-
ables (pH, initial concentration, dosage, and residence time) was
estimated and statistically validated using an analysis of variance
(ANOVA) test. To identify the conditions of process variables for
which that can result in high removal efficiency, the process opti-
mization is carried out using RSM with highest desirability.
2. Experimental
2.1. Preparation of Fe-GO-Gd
The hydrothermal method is most suitable for nanostructured com-
posite preparation including GO-lanthanide based composites [20]. As
shown in the schematic representation (Scheme 1), the preparation of
Fe-GO-Gd via the preparation of GO from graphite using Hummer's
method [21]. The prepared GO was used for the preparation of the
graphene oxide‑gadolinium oxide (GO-Gd) composite using the hydro-
thermal method. Briefly, 1.0 g of dried GO powder was dispersed into
1 L of deionized water and sonicated for 1 h to form a transparent solu-
tion. The solution pH was adjusted to 12 using 1 M NaOH solution. Then,
30 mL of GdN3O9.6H2O solution (with a 1:5 w/w ratio of Gd:GO) was
added dropwise into the GO solution with continuous stirring for 12 h
at 35 °C. After the solution changed color to pale black, the compound
was collected via centrifugation at 8000 rpm and washed three times
with deionized water. Then, it was dried in a vacuum oven at 60 °C for
12 h to produce pure Gd-GO. The prepared Gd-GO was used for iron
oxide immobilization. Then, Fe(III) solution (5:1 w/w ratio of Fe(III):
Gd-GO) was added to the prepared GO-Gd solution. The solution pH
Scheme 1. The preparation scheme of Fe-GO-Gd.
was adjusted to 10 using 1 M NaOH with continuous stirring. Then,
the solution was heated to 80 °C and continuously stirred for 45 min
until it changed to a dark brown. This solution was centrifuged at
8000 rpm and then dried at 60 °C in a vacuum oven. The synthesized
Fe-GO-Gd was used as an adsorbent in this research study for arsenic
adsorption from synthetic wastewater.
2.2. Adsorption and desorption studies
To determine the optimal process variables and effect of each pro-
cess variable on the adsorption efficiency, batch adsorption experi-
ments were carried out in a 50 mL falcon tube with different ranges
for each process variable. Experiments using a total of 50 mL of As
(V) of different concentrations (Range: 10–70 mg/L) with different ad-
sorbent (Fe-GO-Gd) dosages (Range: 0.1 to 1.0 g/L) at various pH values
(2.0 to 12), were conducted at various time intervals (0 to 420 min) and
room temperature. After the solution reached equilibrium, the solution
was collected using a 0.45 μm membrane syringe filter and the filtrate
metal concentration was evaluated using ICP-OES.
2.3. Modeling studies
To investigate the performance of arsenic removal from aqueous so-
lution using the Fe-GO-Gd nanocomposite as an adsorbent, and under-
stand the inherent adsorption mechanisms, a large number of
experimental runs for different ranges needed to be carried out. The ar-
senic removal efficiency depended on various process variables such as
initial concentration, adsorbent dosage, residence time, and pH. Each
parameter may have a diverse impact on the adsorption process; there-
fore, to investigate the influence of a particular parameter, that param-
eter of interest should be varied, maintaining all other parameters at a
constant value. As we know, the parameters influence the arsenic re-
moval efficiency, and each parameter has a range, this may result in
many permutations and combinations. Conducting experiments with
all these permutations and combinations not only is tedious but also
time consuming and expensive. This procedure may not provide an op-
timized parameter set that results in the maximum removal efficiency.
It may also result in a few experimental runs are redundant and may
not provide valuable information. This, keeping in view the range of
each process parameter and minimizing the number of experimental
runs, an experimental matrix was designed using the design of experi-
ment (DOE) approach [7,22,23]. This approach not only minimizes the
number of experimental runs but also addresses the interaction effects
and thus optimizes the process. Using Response surface methodology
(RSM) with a central composite design (CCD) framework, an optimized
experimental matrix was designed resulting in 30 experiments, as
shown in Table 1. Four independent process variables were segregated
into five levels with a coded value (−2, −1, 0, +1, +2) with star points
−2 (−α) and +2 (+α) selected for each process variable as shown in
Table 2.
 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261 3

Table 1
An optimized experimental matrix with an RSM-CCD framework.

Expt. runs Initial conc, mg/L Adsorbent dosage, g/L pH Residence time, min As (V) removal (%)

55 0.7 8 90 16.633
1

40 0.5 6 150 67.870

2

25 0.7 4 90 88.191
3

25 0.3 4 210 77.244

4

55 0.7 4 210 77.259

5

25 0.3 8 210 26.520

6

55 0.3 4 90 47.084
7

40 0.9 6 150 70.044

8

25 0.3 4 90 69.600
9

40 0.5 6 270 73.529

10

25 0.7 4 210 90.115

11

40 0.5 10 150 38.136

12

40 0.5 6 150 67.895

13

40 0.5 2 150 72.615

14

25 0.7 8 90 45.073
15

40 0.5 6 150 67.501

16

25 0.7 8 210 50.154

17

25 0.3 8 90 20.092
18

40 0.5 6 150 67.207

19

70 0.5 6 150 36.560

20

40 0.5 6 150 67.327

21

40 0.5 6 150 67.741

22

55 0.7 4 90 67.139
23

40 0.5 6 30 50.222
24

55 0.7 8 210 27.268

25

40 0.1 6 150 41.102

26

10 0.5 6 150 83.928

27

55 0.3 8 90 13.358
28

55 0.3 8 210 17.590

29

55 0.3 4 210 58.491

30

Table 2 As the efficiency of As(V) removal depends on the aforementioned

Experimental range and coded levels of selected process variables. four process parameters, the relationship between the response vari-
Variable (factors) Units Design range and coded levels able (As(V) removal, ηAs(V)) and four independent process variables
was identified using the RSM-CCD framework. This framework iden-
−α −1 0 +1 +α
tifies a quadratic relation that can be expressed as follows:
Initial concentration mg/L 10 25 40 55 70
Adsorbent dosage g/L 0.1 0.3 0.5 0.7 0.9 X
k X
k X
k
k−1
Residence time min 30 90 150 210 270 ηAsðVÞ ¼ b0 þ bi Xi þ bii Xi 2 þ ∑i¼1 bij Xi X j þ C
pH 2 4 6 8 10 i i j¼iþ1
4 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261
where Xi and Xj are the independent variables; C is the measurement
error; and b0, bi, bii, and bij are the regression coefficients of constant (in-
tercept value), linear, quadratic, and interactive effects, respectively.
3. Results and discussion
3.1. Characterization
The characterization instruments details reported at ESM†. The
results of (Fig. 1) SEM analysis show the highly porous and micro-
crystalline structure of Fe-GO-Gd with a diameter of ~ 40 nm and
length of ~500 nm. The rod type morphology is mainly due to the
presence of Gd [20]. The porous structure of Fe-GO-Gd is due to
the presence of GO, which provides high surface area thus leading
to higher pollutant adsorption. Furthermore, field emission SEM
indicates the presence of Fe, Gd, O and carbon confirms the purity
and formation of Fe-GO-Gd with nanocrystalline size. Further, the
surface BET analysis results (Table S1 and Fig. S1†) show a surface
area of 138.2 m 2 /g and pore volume of 0.232 cm 3 /g with a
6.68 nm pore diameter, confirming the nanoporous surface mor-
phology of the prepared Fe-GO-Gd composite.
The XRD spectrum (Fig. 2a) shows 2θ: 29.58°, 41.23°, 50.54°
and 80.20° (JCPDS 120797) for Gd2O3 and 2θ:16° for GO and the
remain peaks for iron oxide (in different phases including α-
Fe2O3 and Fe3O4) [24], confirming the prepared Fe-GO-Gd. From
the XRD lines and the Scherer formula, the average crystallite
size of Fe-GO-Gd is 40 nm. FT-IR spectrum (Fig. 2b) indicates
the presence of hydroxyl (3000 to 3400 cm −1 ), carbonyl or
epoxy or ether (1598 to 1757 cm −1 ), and asymmetric aromatic
Fig. 1. (a) SEM images of Fe-GO-Gd collected at various resolutions and (b) FE-SEM images of Fe-GO-Gd with elemental composition via SEM-EDX.
alkenes, –C–C=C– stretching vibration in an aromatic ring (1412
to 1442 cm −1 ) functional groups of GO with metal oxide
stretching sharp peaks in a range from 700 to 900 cm−1 [20,25].
The overall FT-IR spectrum confirms the presence of prepared
Fe-GO-Gd composite having active surface functional groups (–
C=O, –C–O–C–, –OH along with iron oxides, gadolinium oxide
and GO) which may enhance the adsorption removal of
pollutants.
Fig. 2c confirms the presence of two prominent peaks at the
Raman shift, ~1358 and ~1606 cm −1 , shows in the GO Raman
spectrum, corresponding to the D and G bands, respectively.
These peaks alter their position based on their bonding nature
[1,26]. As shown in Fig. 2d, the altering Raman shifts towards
the lower range with the bonding of the metal oxide to GO. In
the GO-Gd composite, the D bond only alters its position to the
lower range, while both the D and G bonds alter in the iron
oxide immobilized GO-Gd composite (Fe-GO-Gd). This means
the GO–Gd interaction is associated with the only sp3 asymmetric
defective carbon atoms [1], whereas for the Fe-GO-Gd, the inter-
actions are associated with both sp2 and sp 3 (D and G) domain
carbon atoms of the GO with the metal oxides (iron and gadolin-
ium oxides). When carefully observed at Fig. 2b, the D to G band
intensity ratio (ID/IG) was high in the Fe-GO-Gd compared to that
of the GO-Gd and GO, indicating the localization of sp 3 defects
within the sp 2 carbon frame upon interaction of the GO with
iron oxide [27,28].
The presence of high-intensity XPS (Fig. 2d) peaks at 1220 eV (Gd-
3d) and 145 eV (Gd-4d), 710.00 eV (Fe 2p3/2), and 725.00 eV (Fe 2p1/
2) with ~285 eV (C1s) and ~585 eV (O1s) indicate the purity and
 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261
Fig. 2. The studies of a) XRD; b) FT-IR spectrum; c) Raman spectrum; d) XPS spectrum; e) high-resolution C1s XPS spectrum; f) high-resolution O1s XPS spectrum; g) high-resolution Fe 2p
XPS spectrum; and h) high-resolution Gd 4d XPS spectrum.
formation of the prepared Fe-Gd-GO composite. Moreover, the high-
resolution XPS spectra (Fig. 2e–h) confirm the presence of surface func-
tional groups, –C=O, –C–C=C–, OH–C=O, Fe2+ and Fe3+ states having
different morphologies and Gd2O3.
3.2. Evaluation of the surface adsorption mechanism
The adsorption of As(V) onto the Fe-GO-Gd surface by the presence
of As(3d) occurs at 46 eV. It was clearly observed that the high resolu-
tion XPS spectrum (Fig. 2e–h), where the surface functional groups –
C=C–, –C=O, –C–O–C–, –C–OH, Fe\\O, and Gd\\O of Fe-GO-Gd com-
posite shifted to a lower range, confirmed that the adsorption process
is mainly due to the interaction of these surface functional groups (–
C=C–, –C=O, –C–O–C–, –C–OH, Fe\\O and Gd\\O) with As(V). In addi-
tion, the adsorption process changed with pH and ionic strength (the
details discussed at Section 3.3) confirming the adsorption process
was due to chemical surface complexation for both adsorbents. The ad-
sorption process may occur through electrostatic interaction and ion ex-
change surface complexation as shown in Fig. 3.
5
3.3. Surface adsorption characteristics
The chemistry of the aqueous phase and adsorbent surface are the
key factors controlling arsenic removal. Here, these factors were evalu-
ated by studying various process parameters such as adsorbent dosage,
metal initial concentration, aqueous solution pH, adsorption time and
interfering ions effect.
As shown in Fig. 4(a), it was observed that the adsorption removal
rapidly increases during the first 45 min, then steadily increases from
45 to 300 min before reaching a plateau after 300 min. The equilibrium
time with maximum adsorption removal was 98.2% and 95.4% for initial
metal concentrations of 10 mg/L and 20 mg/L, respectively. It is ex-
pected that, during the initial stage, there are many freely available ad-
sorption sites on the adsorbent surface for adsorption of metal ions thus
causing rapid adsorption. Later, because of a decrease in freely available
adsorption sites, slow kinetics occur between 45 and 300 min. It is also
observed that the adsorption removal decreases with increase in initial
metal concentration; this may be because of the competition between
metal ions for adsorption sites and an increase in molecular interactions
6 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261

Fig. 3. Plausible As(V) adsorption mechanism onto the Fe-GO-Gd composite.

of metal ions. The overall studies conclude that the optimized equilib-
rium time was approximately 300 min.
The As(V) adsorption removal with adsorbent dosage is shown in
Fig. 4(b). As expected, the As(V) removal % rapidly increases from
16.3 to 98.0% as the dosage increased from 0.1 to 1.0 g/L. Then, it reaches
a plateau as dosage increases to N1.0 g/L. However, the specific adsorp-
tion capacity (qe, mg/g) decreases with an increase in adsorbent dosage;
this can be attributed to aggregation among the adsorbent molecules in-
creasing via intramolecular interaction [29,30].
The pH of the aqueous solution is a significant factor that underlines
the surface adsorption process. Fig. 4(c) indicated that a high adsorption
removal of As(V) at pH 2.0, then the adsorption removal slowly de-
creases as the solution pH increases from 2.0 to 6.0. When the pH in-
creases from 7.0 to 10.0, the adsorption process rapidly decreases and
then reaches a plateau between pH 10.0 and 12.0. These results can be
explained based on the adsorbent zero-point charge pH (pHzpc: 5.98)
(Fig. S2) and As(V) speciation with solution pH. As(V) occurs as an an-
ionic species (H2AsO− 4 at pH = 2 to 6, HAsO4
2−
at pH = 6 to 10, and
AsO3−
4 at pH = 10 to 14) in a wide range of pH conditions. The adsor-
bent surface is positive at pH b pHzpc = 5.98 as shown in Eq. (1),
which is favorable for adsorption of anionic H2SO− 4 species of As
(V) via electrostatic interaction showing higher adsorption than that

Fig. 4. The effect adsorption factors on As(V) removal by a) time, b) adsorbent dosage, c) solution initial pH, and d) metal equilibrium concentration.
 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261 7

of other pH conditions. However, with an increase in aqueous solution repulsion, can take place as shown in the following equations:
pH from pH 2.0 to 6.0, the arsenate adsorption removal slowly decreases
because of the slight decrease in the number of positive charge sites on X−OH þ H3 Oþ ðAcidicÞ→X−OH2 þ þ H2 O ðpH≤pHzpcÞ ð1Þ
the adsorbent surface. An increase in aqueous solution pH (pH ≤ pHzpc)
causes a slight electrostatic repulsion between adsorbent surface X−OH þ OH− ðBasicÞ→X−O− þ H2 O ðpH≥pHzpcÞ ð2Þ
charges and the arsenic species H2AsO− 4 . The adsorption removal rap-
idly decreases from pH 7.0 to 10.0 (pH N pHzpc) because of the increase
XOH þ H2 AsO4 − ↔XHAsO4 − þ H2 O at pH ¼ 2:0 to 6:0 ð3Þ
in electrostatic repulsion between the net negative charge adsorbent
2− 2−
surface (as shown in Eq. (2)) and anionic arsenate species HAsO2− 4 .
XOH þ HAsO4 ↔XAsO4 þ H2 O at pH ¼ 6:0 to 10:0 ð4Þ
However, at a pH above 6.0 (NpHzpc), significant adsorption capacity
is observed is due to electrostatic interaction between gadolinium
oxide (Gd2O3) of nanocomposite with arsenic species, AsO3− XOH þ AsO4 3− ↔XOH Gd2 O3 þ AsO4 3− at pH N10:0 ð5Þ
4 .
From the results and analysis, it can be presumed that the As
(V) surface complexation through hydrogen bonding or ion-exchange The overall results of pH indicate that the adsorption process is car-
of adsorbent surface functional groups along with electrostatic ried out by both electrostatic and surface complexation mechanisms.

Fig. 5. (a–f) Interaction effect of all the process variables on As(V) removal efficiency.
8 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261
The adsorption capacity increases as the equilibrium concentration in-
creases as shown in Fig. 4(d). However, a relatively high adsorption capacity
was observed at a low initial concentration. This may be because of the low
in competition between metal ions for large active sites at the surface at low
metal concentration. The effect of in interfering cations and anions effect on
As(V) removal were also investigated (see Fig. S3) and analysis is presented
in ESM. The results found that the competitive adsorption between the an-
ions SO2− 3− 2–
4 , PO4 , and CO3 and arsenate for the active surface sites leads to a
significant decrease in adsorption removal.
3.4. RSM analysis
Experimental runs were performed as per the experimental design
matrix (Table 1), and the corresponding response (%As(V)) for each
run was evaluated. This design matrix was formulated in an aesthetic
framework, where the interaction effect of each variable on the re-
sponse was investigated in a three-dimensional cubical network. This
network monitors the interactive effect of process variables when
used in combination that influences the characteristics of the system.
The interaction plots of initial concentration and dosage on the removal
efficiency (ηAs) (Fig. 5(a)) observed that when maintaining the dosage
at 0.30 g/L, the initial concentration increase from 25 mg/L to 55 mg/L
resulted in a lower removal efficiency, decreasing from 65% to 48%. A
similar trend is observed for a constant adsorbent dosage of 0.7 g/L
and with the same increase in initial concentration. These interaction
profiles thus indicate that the removal efficiency is directly proportional
to the dosage and inversely proportional to the initial concentration.
From the interaction plots of initial concentration-dosage vs. ηAs
(Fig. 5(a)), initial concentration-pH vs. ηAs (Fig. 5(b)), and initial
concentration-Time vs. ηAs (Fig. 5(c)), it can be observed that adsorption
removal efficacy is directly proportional to the adsorbent dosage, pH,
and residence time, whereas it is inversely proportional to the initial
concentration. They are mathematically represented as follows:
ηAs %α adsorbent dosage; pH and residence time
ηAs %α 1=initial concentration
The interaction plots of dosage–pH vs. ηAs and dosage–time vs. ηAs
are shown in Fig. 5(d) and (e), respectively. From these two plots, it
was observed that the removal efficiency is directly proportional to
the dosage and residence time but inversely proportional to pH and
mathematically represented as follows:
ηAs %α adsorbent dosage and residence time
ηAs %α 1=pH
The interaction plot of pH–time vs. ηAs is shown in Fig. 5(f); this plot
shows that the removal efficiency decreases at a higher pH, whereas a
higher residence time always results in higher efficiency. These profiles
thus infer that there is a significant interactive effect of each parameter
on the overall performance of As(V) removal using a Fe-GO-Gd nano-
composite adsorbent during the batch adsorption process. Therefore,
overall higher removal efficiency is favored by a higher dosage and
time and lower initial concentration and pH.
To evaluate the perturbation impact of the process of each variable on
the response, each variable was perturbed around its reference point as
shown in Fig. 6. In this plot, each process variable is perturbed around
its reference value of 40.0 mg/L, 0.5 g/L, 6.0, and 80 min for initial concen-
tration, dosage, pH, and residence time, respectively. It was observed from
this analysis that each process variable behaves differently in overall As
(V) removal. This variation is because of the interactive effect of process
variables and their effect on process mechanisms. For example, if the ini-
tial concentration (A) is increased from the reference value of 40 mg/L re-
sults in lower As(V) removal whereas lowering its value below the
Fig. 6. Effect of perturbation of each process variable: A: initial solution concentration
(40.0 mg/L) B: adsorbent dosage (0.50 g/L), C: pH (6.0). D: residence time (150 min).
reference point enhances removal efficiency. It was observed that any
small increment in adsorbent dosage (B) greater than its reference
value enhances removal efficiency, whereas any minor decrement from
its reference value results in lower removal efficiency. This is an exciting
trend to validate the behavior of the variation of dosage on arsenic re-
moval. Likewise, the effect of pH on As(V) removal was also studied. Re-
markably, this process variable seems to be highly sensitive and effects
the removal efficiency with marginal perturbation around its reference
value of 6.0. In contrast to the aforementioned three process variables,
the residence time was found to have a lower or negligible impact on
As(V) removal when perturbed around its reference value of 150 min.
Therefore, these profiles further signify the impact of each parameter
and their sensitivity concerning the percentage removal of As(V) from
the aqueous environment using the Fe-GO-Gd nanocomposite.
The 3D response surfaces and contours for different independent pro-
cess variables (pH, initial concentration, dosage, and residence time),
concerning arsenic removal efficiency, are shown in Fig. 7. These plots
demonstrate the related fitted response surface plots for the optimal de-
sign of the adsorbent, the Fe-GO-Gd composite for As(V) removal (%)
from aqueous solutions. The interaction plot of the initial concentration
– adsorbent dosage vs. efficiency (at a constant pH and residence time)
is shown in Fig. 7(a). It was observed that an increase in the adsorbent
dosage from 0.3 g/L to 0.7 g/L results in removal efficiency enhancement
from 60% to 90%, in contrast to the removal efficiency decrease as the ini-
tial solution concentration increases. Similar behavior was also ob-
served with initial concentration – residence time vs. efficiency (at
a constant pH and adsorbent dosage) as shown in Fig. 7(c). This
trend can be attributed to the increased surface area [31] and the ac-
cessibility of more vacant active sites at a higher amount of adsor-
bent enhancing the removal efficiency. The contour plot (Fig. 7(b))
for initial concentration – pH vs. efficiency (at a constant residence
time and adsorbent dosage) shows a different behavior. This contour
thus confirms that removal efficiency is inversely proportional to ini-
tial concentration and pH, which means that higher removal efficacy
can be achieved at a lower pH and lower initial concentration. Simi-
lar observations can be derived for the other plots dosage – pH vs. ef-
ficiency (Fig. 7(d)), dosage – time vs. efficiency (Fig. 7(e)), and time –
pH vs. efficiency (Fig. 7(f)). The curvature nature of these plots
shows the intensity of the interaction among the independent pro-
cess variables.
 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261
To identify a reliable adsorption processing model for As
(V) removal prediction, an analysis of variance (ANOVA) test was
performed on the experimental data obtained under different pro-
cess conditions. The RSM approach along with ANOVA provided a
quadratic model capturing the interaction of individual process var-
iables on the response prediction. The identified quadratic model is
expressed as follows:
 
ηAs % ¼ −1:760 þ 0:548  A þ 184:496  B þ 5:014  C þ 0:291
 D−0:590  A  B þ 0:017  A  C þ 0:001  A  D−1:362
 B  C−0:010  B  D−0:002  C  D−0:015
 A2 −111:685  B2 −1:129  C2 −0:001  D2 ð6Þ
The estimated coefficients using ANOVA and the corresponding de-
grees of freedom, the sum of squares, p value, and F value, are listed in
Table 3. The importance of each term in the quadratic model has to be
determined using the p value and F value. The statistical significance
of each term at 95% confidence is indexed by its p value (b0.05). If the
magnitude of the p value is smaller, this indicates that the
Fig. 7. Contours plots of process variables and their effect on removal efficiency in three-dimensional space.
9
corresponding coefficient is highly significant. The model fit is deter-
mined based on the coefficient of determination (R2 = 0.889), signify-
ing that the aforementioned quadratic model can describe 88.9% of
the variability in the response. The adjusted R2 value is 0.853, indicating
that only 15% of the total variation cannot be explained using this
model. Another important statistical measure is the lack of fit (LOF)
measure. This measure explains the critical failure of the model in
representing experimental data in the domain that are excluded in the
regression model. The LOF of 1642.16 with a p value of b0.0001 implies
that it is very significant. The performance of the quadratic model
(Eq. (6)) predictions against the experimental values is shown in
Fig. 8. This scatter plot shows the higher value for the coefficient of de-
termination. Therefore, this regression model as given in Eq. (6) can be
used to predict As(V) removal both within and outside the experimen-
tal range of the process variables. Based on the RSM model, the highest
As(V) removal efficiency of 94.8% can be achieved at the optimal condi-
tions of Initial concentrations, adsorbent dosage, pH and residence time
of 25.0 mg/L, 0.70 g/L, 4.0 and 187 min respectively. These optimum re-
sults are chosen based on highest desirability of 0.998.
10 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261

Table 3
ANOVA of the identified quadratic model via an RSM-CCD framework.

Source Sum of squares df Mean square F-value p-Value

Model 13,146.7 14 939.05 8.58 b0.0001 Significant

A-Initial concentration 2338.48 1 2338.48 21.35 0.0003 Significant
B-Dosage 1500 1 1500 13.7 0.0021 Significant
C-pH 7610.98 1 7610.98 69.5 b0.0001 Significant
D-Time 451.41 1 451.41 4.12 0.0604
AB 50.06 1 50.06 0.4572 0.5092
AC 4.19 1 4.19 0.0382 0.8476
AD 14.66 1 14.66 0.1339 0.7195
BC 4.75 1 4.75 0.0434 0.8378
BD 0.2381 1 0.2381 0.0022 0.9634
CD 1.39 1 1.39 0.0127 0.9117
A2 298.65 1 298.65 2.73 0.1194
B2 547.41 1 547.41 5 0.041 Significant
C2 559.59 1 559.59 5.11 0.0391 Significant
D2 229.37 1 229.37 2.09 0.1684
Residual 1642.58 15 109.51
Lack of fit 1642.16 10 164.22 1967.21 b0.0001 Significant
Pure error 0.4174 5 0.0835
Cor total 14,789.3 29

3.5. Stability and re-usability studies was very much comparable to that of the other reported materials.
The overall results suggest that Fe-GO-Gd can be considered as a prom-
The efficacy of stability and reusability of the materials is shown in ising adsorbent for efficient As(V) removal.
Fig. 9. The desorption of As(V) from the Fe-GO-Gd was carried out
using 0.1 M of NaOH. Fig. 9 shows that the adsorption capacity of Fe-
4. Conclusions
GO-Gd is stable up to 3 cycles with a N 90% adsorption removal, but it
decreases to a lower range (b65%) after the 4th cycle. This may attrib-
In this study, a novel nanocrystaline Fe-GO-Gd adsorbent was synthe-
uted a change in surface morphology by the leaching of iron and gado-
sized for adsorption removal of As(V). Up to 99.9% of As(V) adsorption re-
linium ions or surface functions after the 4th cycle. The leached metal
moval was achieved using the present nanocomposite. The adsorption
ions (Fe2+/Fe3+ and Gd3+) are at US-EPA acceptable levels. Hence, the
process was optimized using the RSM with a central composite design
present material Fe-GO-Gd can be successfully used for arsenic removal
(CCD) framework. The interaction effects study showed that the adsorp-
as a beneficiary to the society.
tion removal efficacy is directly proportional to the adsorbent dosage,
pH, and residence time whereas it is inversely proportional to the initial
As(V) concentration. The quadratic model, identified using the ANOVA
3.6. Future perspective and advantages of present work
test, significantly captures the interaction of individual process variables
on the response prediction and results in a high coefficient of determina-
This study was aimed to understanding the adsorption behavior of a
tion. Based on the RSM model, the highest As(V) removal efficiency of
Fe-GO-Gd for arsenate adsorption from potable water. Given the advan-
94.8% can be achieved at the optimal conditions of Initial concentrations,
tages of the present material characteristics and performance for the
adsorbent dosage, pH and residence time of 25.0 mg/L, 0.70 g/L, 4.0 and
real application, Fe-GO-Gd can find many applications in the future.
187 min respectively. The results regarding stability and reusability con-
Moreover, the prepared nanocomposite can be quickly recovered
firm that the prepared nanocomposite can be quickly recovered using
using an external magnetic field and can be successfully re-used up to
an external magnetic field and can be successfully re-used for 3 cycles
4 cycles without loss of its original adsorption capacity. To further vali-
without loss of its original adsorption capacity.
date the potentiality of prepared Fe-GO-Gd as an adsorbent, its perfor-
mance (maximum adsorption capacity) was compared to that of
previously reported similar materials (Table 4) for As(V). These results CRediT authorship contribution statement
show that the maximum adsorption capacity of the present adsorbent
L.P. Lingamdinne: Conceptualization, Data curation, Formal analy-
sis, Resources, Writing - original draft. J.-S. Choi: Data curation, Formal

Fig. 8. Comparison of model predictions against actual experimental values. Fig. 9. Recycling and re-usability study of Fe-Gd-GO.
 L.P. Lingamdinne et al. / Journal of Molecular Liquids 299 (2020) 112261 11

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