Groundwater for Sustainable Development 11 (2020) 100417

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Groundwater for Sustainable Development

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Research paper

Chemically treated Lawsonia inermis seeds powder (CTLISP): An

eco-friendly adsorbent for the removal of brilliant green dye from
aqueous solution
Rais Ahmad *, Khalid Ansari
Environmental Research Laboratory, Department of Applied Chemistry, Faculty of Engineering & Technology, Aligarh Muslim University, Aligarh, 202002, India

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

Keywords: The present paper deals with the preparation of a novel low-cost and eco-friendly chemically treated lawsonia
Lawsonia seeds inermis seed powder (CTLISP) as adsorbent and was further explored for the removal of brilliant green (BG) dye
brilliant green (93%) from aqueous solution. The adsorbent was characterized by various techniques such as FTIR, EDX, SEM
Langmuir
and TEM. Effects of various parameters such as concentration, pH, doses, contact time was carried out. The
breakthrough capacity
maximum adsorption capacity 34.96 mgg 1 was found to be at 50 � C. The equilibrium was attained in 180 mints
and the experimental data were elucidated for isotherms and kinetic studies. The results exhibited that the data is
best fitted for the Langmuir isotherm with maximum (R2) value of 0.990 and pseudo-second order kinetics with
maximum (R2) value of 0.998. The thermodynamic parameters such as ΔH0, ΔG0 and ΔS0 were also evaluated
and the results showed the process to be endothermic, spontaneous in nature. The desorption study showed that
84% of the adsorbed BG could be desorbed by using 1 M oxalic acid as eluting agent. The breakthrough and
exhaustive capacities were found to be 12.5 and 45.0 mg g 1, respectively. In order to make the process more
economical and feasible the regeneration studies were also carried out and the adsorbent can be reused up to fifth
cycle successfully. Therefore, the present low-cost adsorbent (CTLISP) has excellent regenerative capability and
gives high monolayer adsorption capacity as compared to others various adsorbent reported in literature.
Moreover, the material has been proved to be a promising adsorbent for treatment of BG dye from aqueous
solution.

1. Introduction
Pollution has become a monstrous brawl in environment all over the
world due to the presence of dyes, organic pollutants and metals in
water which affect the human life and posing hazard to living organism
(Khan Rao and Khatoon, 2016). Large amounts of waste water are dis­
charged from variegated industries peculiarly textile, leather, cosmetics,
food technology, hair colouring, paper and printing production etc
(Akter et al., 2016). Dyes that are discharged from these industries are
highly toxic and can cause permanent scathe to the eyes and skin of
humans and animals (Ghaedi et al., 2011; Kismir and Aroguz, 2011).
Due to reduced light penetration, the dyes affect photosynthesis activity
in aquatic environments, which is a specific form of pollution from dyes
(Mane and Babu, 2011).
Brilliant Green dye is used in large scale in textile dying and paper
printing industry. Especially wood and fibre objects are dyed using
Brilliant Green. This dye is risk full in the case of skin contact, eye
contact and ingestion. It is considered highly toxic to the lungs, through
inhalation (Kismir and Aroguz, 2011). The toxic and hazardous sub­
stances produced by dyes after undergoing oxidation and reduction in
water further increases the health hazard and therefore needs urgent
attention for their removal from waste water.
Several treatment methods have been used such as adsorption, oxi­
dation–ozonation, biological treatment, coagulation–flocculation and
membrane process for the removal of dyes and other toxic chemicals
from the effluents (Walker et al., 2003). Dyes have low biodegradability
therefore conventional biological treatment methods are not very
effective in treating dye waste water. It is often treated by physical or
chemical process. However, these processes cannot be used to treat the
wide range of dye waste waters due to cost and disposal problems (Garg
et al., 2003). Adsorption techniques is a well-known and preferred to
other removal techniques because it is more inexpensive, convenient

* Corresponding author. Department of Applied Chemistry Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh, 202002, UP, India.
E-mail address: rais45@rediffmal.com (R. Ahmad).

https://doi.org/10.1016/j.gsd.2020.100417
Received 10 February 2020; Received in revised form 23 May 2020; Accepted 26 May 2020
Available online 31 May 2020
2352-801X/© 2020 Elsevier B.V. All rights reserved.
R. Ahmad and K. Ansari
and is capable to efficiently treat dyes in a more concentrated form
(Annadurai et al., 2002a,2002b). Natural materials or certain waste
from industrial or agricultural operations is one of the resources for low
cost adsorbents. In the past few years, various low-cost materials such as
acid treated almond peel, silica, clay materials, bark/tannin rich mate­
rials, waste orange peel, banana pith and agricultural wastes such as
apricot waste, soya meal hull, rice husk, sugar beet pulp, and wheat bran
have been employed successfully for the removal of various hazardous
chemicals and dyes from waste waters (Ahmad and Mondal, 2009;
Kumar et al., 2014b; Mittal et al., 2008). It is now greatly acknowledged
that adsorption using low-cost adsorbents is an effective and economical
method for water decontamination. Many non-conventional low-cost
adsorbents, including natural materials could be used as sorbents for the
removal of dyes from aqueous solution and these materials have quite
high potential to adsorb dyes from waste water (Crini, 2006; Khan Rao
and Khatoon, 2016). Now there is further need to explore new,
economical, easily available and highly effective adsorbents for the
removal dyes from waste water at large scale.
Lawsonia inermis, also known as hina, the henna tree, the mignonette
tree, and the Egyptian privet, is a flowering plant and the sole species of
the genus Lawsonia. It is the source of the dye henna used to dye skin,
hair and fingernails, as well as fabrics including silk, wool and leather.
Henna is a tall shrub or small tree, standing 1.8–7.6 m tall (6–25 ft).
Henna fruits are small, brownish capsules, 4–8 mm (0.16–0.31 in) in
diameter, with 32–49 seeds per fruit, and open irregularly into four
splits.The henna plant is native to northern Africa, Asia, and northern
Australia, in semi-arid zones and tropical areas. It produces the most dye
when grown in temperatures between 35 and 45 � C (95 and 113 � F).
During the onset of precipitation intervals, the plant grows rapidly,
putting out new shoots. Growth subsequently slows. The leaves gradu­
ally yellow and fall during prolonged dry or cool intervals. It does not
thrive where minimum temperatures are below 11 � C (52 � F). Tem­
peratures below 5 � C (41 � F) will kill the henna plant (Kumar et al.,
2005).
Lawsonia inermis seeds powder (LISP), is a novel low-cost and
abundantly available in India. The LISP was further treated chemically
with orthophophoric acid (CTLISP) for the removal of brilliant green
(BG) dye (93%) from aqueous solution. The CTLISP was found to remove
(93%) brilliant green (BG) dye from the aqueous solution.The desorp­
tion study showed that 84% of the adsorbed BG could be desorbed by
using 1 M oxalic acid as eluting agent. The breakthrough and exhaustive
capacities were found to be 12.5 and 45.0 mg g 1, respectively. In order
to make the process more economical and feasible the regeneration
studies were also carried out and the adsorbent can be reused up to fifth
cycle successfully. Therefore, the present low-cost adsorbent (CTLISP)
has excellent regenerative capability and gives high monolayer
adsorption capacity as compared to others various adsorbent reported in
literature (See Table 5). Moreover, the material has been proved to be a
promising adsorbent for treatment of BG dye from aqueous solution.
Present study was aimed to use chemically treated Lawsonia inermis
seed powder (CTLISP) as an adsorbent for the removal of BG dye from
aqueous solution. The effects of various parameters such as concentra­
tion, contact time, pH, adsorption kinetics, adsorption isotherms, ther­
modynamics and adsorption mechanisms were studied in detail. In order
to make the process more economical and feasible, the exhusted mate­
rial were further desorbed and regenerated.
2. Materials and methods
2.1. Materials
Lawsonia inermis seeds were collected from the nearby city, Jalesar,
U.P., India. Seeds were crushed to get fine powder and further sieved to
300-150 μm particle size. Powder of seeds was washed several times
with double distilled water to remove adhering filth and dust particles
and then dried in an oven at 80 � C for 8 h.
2
Groundwater for Sustainable Development 11 (2020) 100417
2.2. Treatment of adsorbent
The adsorbent was treated chemically by using orthophosphoric acid
H3PO4 (0.1N) solution. For this, an accurately weighed 30 g of dried
Lawsonia inermis seeds powder was soaked in 500 mL of modificant so­
lution and thoroughly shaken (300 rpm) for 4 h at room temperature.
The mixture was left overnight and then filtered and rinsed several times
with DDW till the washed solution was neutral. Chemically treated
Lawsonia inermis seeds (CTLISP) adsorbent was then dried at 80 � C for 6
h and stored in an air tight container, to avoid moisture for further use.
2.3. Preparation of stock solution
The stock solution of 1000 ppm was prepared by dissolving accu­
rately weighed amount of brilliant green (BG) dye in 1 L of double
distilled water. The stock solution was further diluted for the experi­
mental solution of desired concentration using double distilled water.
The concentration of equilibrium solutions was measured using UV–Vis
spectrophotometer (T70, UV/VIS spectrometer, PG Instruments, UK) for
BG dye at λmax - 625 nm.
2.4. Batch adsorption studies
The adsorption studies were carried out using batch process. The
effect of various experimental parameters such as concentration
(20–100 ppm), pH (2–11), contact time (5–360 min), and temperature
(30–50 � C) on the adsorptive removal of adsorbate ion were studied. 0.2
g of adsorbent was taken in a series of 100 ml conical flask with 20 mL of
BG dye solution of desired concentration with subsequent shaking for
optimum contact time and pH was maintained using 0.5 M NaOH and
HCl solution. The adsorbate was filtered using Whatman Filter paper 1.
The % adsorptions of BG dye and adsorption capacity, qe (mgg 1) of the
adsorbent at equilibrium were calculated from the following
relationships.
ðCi Ce Þ
%removal ¼ � 100 (1)
Ci
qe ¼
ðCi Ce ÞV
(2)
W
where, Co (mgL 1) is initial dye concentration, Ce (mgL 1) is final
concentration at equilibrium, qe is the adsorption capacity (mgg 1), V is
the volume of the solution in liter (L) and m (g) is the mass of the
adsorbent (Mahida and Patel, 2016).
2.5. Selectivity study
The selective nature of low-cost adsorbent i.e. chemically treated
powder of Lawsonia inermis seeds (CTLISP) were studied for Congo red,
crystal violet, Methylene blue, Patent blue and Brilliant green dye. The
% removal for these pollutants were found to be in the order as follows:
Brilliant green (93.88%) ˃Methylene blue (87.11%) ˃ Crystal violet
(73.34%) ˃ Patent blue (60%) ˃ Congo red (56.9%). Therefore, BG dye
was selected for further detailed experimental studies.
2.6. Point of zero charge
Solid addition method was used for the determination of point of
zero charge study (Rao et al., 2016). 20 ml of 0.1 M KCl solution was
transferred in a series of 100 ml conical flasks with pH values ranging
from 2 to 11. The pH was adjusted using 0.5 M NaOH and HCl solutions.
0.2 g of adsorbent was then transferred into each flask and the mixture
was left for 24h to attain equilibrium. After equilibrium, solutions were
filtered and the final pH was recorded by pH meter. The point of zero
charge was obtained by plotting ΔpH values versus initial pH (pHi).
R. Ahmad and K. Ansari Groundwater for Sustainable Development 11 (2020) 100417

2.7. Breakthrough studies Table 1

EDX analysis of Lawsonia inermis seeds powder before treatment, after treatment
0.2 g of CTLISP adsorbent was transferred in a glass wool supported and after adsorption of BG dye.
column (0.6 cm internal diameter). Then, 400 mL solution of BG dye (50 Elements Before treatment After treatment After adsorption
ppm) was passed through the column at a flow rate of 1 mLmin-1. The Weight Atomic Weight Atomic Weight Atomic
effluent was collected in 10 mL fractions. Then, each fraction was % % % % % %
analyzed using UV–Vis spectrophotometer. The breakthrough curve was
C 65.24 71.44 60.30 66.99 54.04 60.43
plotted between Ce/Co against volume of effluent (mL). O 34.75 28.56 39.43 32.89 37.72 31.67
P – – 0.27 0.12 – –
N – – – – 8.23 7.90
2.8. Desorption studies Total 100.00 100.00 100.00 100.00 100.00 100.00

The desorption and regeneration studies for BG dye were examined

3.1.3. FTIR analysis
by batch process using various desorbing agents such as H2O, 0.1M HCl,
The functional groups present on the surface of raw LISP, CTLISP and
0.1M NaOH, 0.1M CH3COOH and (CH2COOH)2 at room temperature for
after adsorption of BG dye were identified by FTIR analysis of the
24 h.
sample. The FTIR spectra of raw LISP, after treatment CTLISP and after
adsorption are shown in Fig. 2(a–c). In the FTIR spectra of raw LISP
3. Results and discussion (Fig. 2a), the broad and strong peak observed at 3401 cm 1 was aroused
due to stretching vibrations of –OH groups (Rao and Kashifuddin, 2014).
3.1. Characterization The two sharp and intense peaks at 2930 and 2857 cm 1 were assigned
due asymmetric and symmetric stretching vibration of –CH2 (Hasan and
3.1.1. Morphology study (scanning electron and transmission electron Ahamd, 2019). The absorption peak at 1652 cm 1 was obtained due to
microscope) the carboxylate anions (-COO-) (Rao and Ikram, 2011). A very small and
The SEM images of low-cost adsorbent of LISP before treatment weak peak appearing at 1463 cm 1 was attributed to N–H stretching
Fig. 1a, after chemically treatment Fig. 1b and after adsorption Fig. 1c vibrations in amide (Ma et al., 2014). A strong peak at 1035 cm 1 was
respectively were obtained using model JSM (6510LV, JEOL, Japan).
The surface morphology of raw LISP seems to be less porous compare to
the surface of chemically treated LISP. So, the size and volume of the
pores increased and functional groups on the surface of the adsorbent
also improved after treatment. The surface of chemically treated
adsorbent after adsorption of BG dye becomes denser and smoother with
significant change in surface morphology.
The particle size of the CTLISP was obtained using Transmission
electron microscope (TEM) (TEM, JEM 2100, JEOL, Japan). The TEM
image of CTLISP (Fig. S1) and the image shows the size between 28.9 nm
and 53.5 nm.

3.1.2. EDX analysis

The adsorption of (BG) dye onto CTLISP was further confirmed by
EDX analysis showed in Fig. S2 (a-c). The EDX analysis of raw LISP,
chemically treated powder of LIS and after adsorption BG dye loaded
adsorbent were reported in Table 1. The EDX spectrum of raw LISP
confirmed that carbon and oxygen were major constituents of the
adsorbent. The presence of phosphorous element in the spectra of
chemically treated adsorbent confirmed that treatment of adsorbent
with orthophosphoric acid (H3PO4) was successful. Peak of the element
Nitrogen in the spectra after adsorption confirmed the adsorption of BG
Fig. 2. FTIR spectra (a) raw LISP (b) CTLISP (c) CTLISP after BG adsorption.
dye onto the surface of treated adsorbent.

Fig. 1. SEM micrograph (a) raw LISP (b) CTLISP (c) CTLISP after BG adsorption (Magnification: 1500�; Scale: 10 μm).

3
R. Ahmad and K. Ansari Groundwater for Sustainable Development 11 (2020) 100417

attributed to C–N stretch of aliphatic amines (Hossain et al., 2014). The solution (50 ppm) varying amount of adsorbent (0.1–1.0 g) was added at
short and broad peak obtained at 607 cm 1 was assigned due to room temperature. Fig. (S6) represents the rate of adsorption, when the
metal-oxide bond as oxide of metal generally give absorption bands amount of dose increased the percent of adsorption increased while
below 1000 cm 1 resulting from inter-atomic vibrations (Anandan and adsorption capacity decreased on increasing the amount of adsorbent
Rajendran, 2011; Wang et al., 2013). In FTIR graph of CTLISP (Fig. 2b), dose, which was due to the availability of excessive adsorption sites
showed shifting in absorption peaks around 3401 cm 1, 2930 cm 1, causing the decrease in dye by a unit mass of the adsorbent as some of
2857 cm 1, 1652 cm 1, 1463 cm 1, 1035 cm 1 and 607 cm 1. These the adsorption sites remained unoccupied at higher adsorbent dose
peaks have been shifted to 3383 cm 1, 2894 cm 1, 2826 cm 1, 1622 (Asgarzadeh et al., 2016).
cm 1, 1426 cm 1, 1004 cm 1 and 594 cm 1 respectively, changes in the
wave number of all these peaks indicated that after the chemical treat­
ment of adsorbent with H3PO4 acid fetch some changes in the functional 3.3. Adsorption isotherm
groups of LISP. In the FTIR spectra after the adsorption of BG dye on the
surface of CTLISP (Fig. 2c), absorption peaks around 3383 cm 1, 1622 Several adsorption isotherms models namely, Langmuir Eq. (3),
cm 1 and 594 cm 1 were shifted to 3395 cm 1, 1616 cm 1 and 600 Freundlich Eq. (4), Temkin Eq. (5) and Dubinin-Radushkevich (D-R) Eq.
cm 1 respectively, these changes showing successful interaction of BG (6) were studied to found out the nature of adsorption process (Ahmad
dye with the surface of sample. and Mirza, 2017a). Adsorption isotherm experiments of BG dye onto
CTLISP were carried out using initial BG concentration (20–100 ppm),
3.1.4. XRD analysis 0.2 gm (dose), contact time 180 min, pH-6 with temperature ranging
The crystallinity of the CTLISP was examined using instrument X-ray from 30 � C to 50 � C.
diffractometer (LabX, XRD-6100, SHIMADZU). Fig. S3 (a-b) represents Langmuir isotherm model (Langmuir, 1918);
the XRD spectra of LISP and CTLISP, characteristic peaks of LISP
1 1 1
(Fig. S3) obtained at 2 theta values of 44.09� , 64.390 and 77.59� . Fig. (S ¼ þ (3)
qe Ce ⋅bqm qm
3b) shows the intensity of the material increases after the chemically
treatment of the adsorbent by H3PO4 and there appear certain peaks in where, qm is Langmuir monolayer adsorption capacity (mgg 1
), and b is
the XRD spectra of CTLISP at 43.95� , 64.39� and 77.59� . The XRD a constant related to adsorption energy (Lmg 1).
pattern of both LISP and CTLISP shows the sharp peak and adsorbent Freundlich isotherm model (Freundlich, 1906);
appeared to be crystalline in nature.
1
log qe ¼ log KF þ log Ce (4)
3.2. Adsorption behaviour of CTLISP n
1
Where, KF is a constant related to adsorption capacity (mgg )
3.2.1. Effect of pH and point of zero charge
(Lmg 1)1/n and n is another Freundlich constant.
The adsorption of BG dye on CTLISP was examined in the pH range
Temkin isotherm model;
2–8. 20 mL of 50 ppm dye solution was taken in each 100 mL conical
flask and the desired pH of the solution in each flask was adjusted by qe ¼ B ln A þ B ln Ce (5)
adding 0.5 M NaOH and HCl solutions. 0.2g adsorbent was then added in
each flask and the mixture was left to obtained equilibrium. Fig. (S 4a) Where A (gL 1) and B (Jmol 1
) are Temkin constants.
shows the influence of pH on adsorption rate of BG dye on CTLISP. The D-R isotherm model;
adsorption rate increased on increasing pH and reached its maximum ln qe ¼ ln qm β ε2 (6)
value above 93% at pH 6. While after pH 6, rate of adsorption decreased
on further increasing the pH of dye solution. So, pH value of 6 was where, β (molK 2 J 2) is the isotherm constant related to parameter E
selected as optimum pH for the adsorption of BG dye. (mean free energy per molecule of adsorbate) (kJ mol 1) as
Fig. (S 4b) represents the point of zero charge of CTLISP was found to
be 3. As pH˃ pHpzc, the surface of CTLISP was negatively charged and 1
E ¼ pffiffiffiffiffi (7)
hence, adsorption of BG dye onto the surface of adsorbent has been 2β
increased (Ahmad and Haseeb, 2012). Inferring from results, pH 6 was
where ϵ is model constant representing the polyanyi potential. The value
selected for further experimental studies.
of ε can be calculated as
� �
3.2.2. Effect of contact time 1
ε ¼ RT ln 1 þ (8)
In adsorption process, contact time is one of the vital parameters that Ce
directly affect the adsorption kinetics. To determine the optimum time
for attainment of equilibrium, batch studies were performed using 0.2 where R is the gas constant (8.314 J mol 1), and T is the absolute
gm adsorbent with 20 mL of BG dye solution (50 ppm) in a time range of temperature (K) (Foo and Hameed, 2010).
5–720 min. The amount of adsorbed BG dye was calculated by method of Experimental data were analyzed at 30, 40 and 50 � C for each
residues using Eq. (2). These quantities are plotted as a function of isotherm parameters and the values of each model were reported in
contact time (min) given in Fig. (S5). The adsorption of BG dye is very Table 2. In Langmuir isotherm, the values of monolayer adsorption ca­
rapid during the first 180 min due to presence of abundant active sites pacity (qm) was found to be 26.45, 29.76, 34.96 mgg 1 at 30, 40 and 50
on the surface of the adsorbent. In the next step, with the continuous �
C temperature, respectively (Fig. 3a). Therefore, according to the re­
decrease in active sites, uptake of BG dye becomes slow and no further sults the high values of correlation coefficient, R2 (0.990) at all studied
change in uptake process was observed after 180 min. So, 180 min was temperature indicated that the Langmuir was the best fitted isotherm
chosen as optimum time for adsorption of BG dye. model and the values of adsorption capacity (qm) implying monolayer
adsorption of BG dye on the surface of CTLISP. In Freundlich isotherm
3.2.3. Effect of adsorbent dose model, the values of n can be used for explain the adsorption was
On the adsorption of BG dye on CTLISP, the effect of adsorbent dose favourable or not. If the value of n lies between 1 and 10, then the
was an important parameter to select the appropriate amount of adsorption indicates favourable adsorption (Ahmad and Mirza, 2017a;
adsorbent for removing the dye from aqueous solution (Du et al., 2012). Zhang et al., 2016). The values of KF and n are reported in Table 2 and
To a series of 100 mL conical flasks each containing 20 mL of BG dye the values of n˃1 were obtained at all temperature, indicating favourable

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R. Ahmad and K. Ansari Groundwater for Sustainable Development 11 (2020) 100417

Table 2 greater than 8 but less than 16 kJ mol 1 then the nature of the process is
Adsorption isotherm parameters for adsorption of BG dye on CTLISP at 30, 40 said to be chemical. E values were found to be 1.926, 1.956 and 1.990
and 50 � C. kJmol-1 summarized in Table 2, at 30, 40 and 50 � C, respectively indi­
Model Parameters Temperature cating physical adsorption of BG dye.
30 0C 40 0C 50 0C

Langmuir b (L g 1) 0.053 0.046 0.038 3.4. Adsorption kinetics

qm (mg g 1) 26.45 29.76 34.96
R2 0.990 0.990 0.990
SD 0.018 0.020 0.021
To carry out the kinetic studies of adsorption of BG dye the initial BG
Freundlich KF (mg g 1) (L 1.315 1.279 1.244 dye concentration was varied at constant temperature (30 � C). Potential
mg 1)1/n rate controlling steps (mass transport and chemical reactions) and the
N 1.118 1.095 1.069 mechanism of adsorption can be explained using various kinetic models
R2 0.978 0.976 0.974
such as pseudo-first order (Eq. (9)), pseudo-second order (Eq. (10)),
SD 0.044 0.047 0.050
Temkin A (L g 1) 0.924 0.947 0.975 intra-particle diffusion model (Eq. (11)) and elovich kinetic model (Eq.
B (J mol 1) 3.879 3.963 4.052 (12)) (Khan and Khan Rao, 2017). The models were expressed by the
R2 0.872 0.864 0.857 following Equations:
SD 1.195 1.235 1.266 Pseudo-first order-
D-R qm (mol g 1) 20.834 21.736 22.623
β (mol K 2 J 2) 13.47 � 13.06 � 12.62 � k1 t
10 8 10 8 10 8 logðqe qt Þ ¼ log qe (9)
1
2:303
E (kJ mol ) 1.926 1.956 1.990
R2 0.879 0.879 0.877 Pseudo-second order-
SD 0.251 0.253 0.254
t 1 t
¼ þ (10)
qt k2 q2e qe
adsorption (Fig. 3b). In Temkin isotherm model, the values of constant A
and B were calculated from the intercept and slope of the linear plots of Intra-particle diffusion-
qe versus ln Ce (Fig. 3c). The values of A and B are listed in Table 2. The qt ¼ Kid t1=2 þ C (11)
constant, A represents binding energy while B represents enthalpy of
adsorption. The Temkin isotherm model is based on two assumptions, Elovich kinetic model-
viz., heat of adsorption would decrease linearly rather than logarithmic qt ¼ A þ B ln t (12)
with the coverage, and its derivation is characterized by a uniform
distribution of binding energies up to some maximum binding energy where, qe, qt both are the adsorption capacity at equilibrium and time (t)
(A.O, 2012). In D-R model, the values of ln qe were plotted against ε2 respectively. k1 (min 1), k2 (gmg 1min 1) are pseudo-first order and
(Fig. 3d) to obtain D-R constants (qm and β). Another important pseudo-second order constants respectively. Kid (mgg 1 min 1/2) is the
parameter of the model is mean free energy, E (kJ mol 1) which is used intraparticle diffusion rate constant and C is the intercept indicating the
to determine the nature of adsorption. If E < 8 kJ mol 1, then the thickness of boundary layer. A (mg g 1 min 1) and B (g mg 1) are
adsorption process is physical in nature and if E value is equal to or Elovich constants (Ahmad and Mirza, 2015).

Fig. 3. Adsorption isotherm (a) Langmuir (b) Freundlich (c) Temkin (d) D-R model for the adsorption of BG onto CTLISP at different temperature.

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R. Ahmad and K. Ansari Groundwater for Sustainable Development 11 (2020) 100417

The parameters of various kinetic models were reported in Table 3. present study, the value of ΔH0 was found to be 10.34 kJ mol 1 indi­
From Fig. 4(a–d), the correlation coefficient (R2) was highest for pseudo- cating physical adsorption or physisorption of BG dye on CTLISP. The
second order model. In addition, the values of qe (cal) obtained from calculated value of E from D-R isotherm model also confirmed that the
pseudo-second order model were much closer to the qe (exp) at all BG dye adsorption on CTLISP to be physical in nature. The ΔG0 values
studied concentration are indicative of better fitness of the experimental were found to be 11.704, 12.353 and 13.148 at 30, 40 and 50 � C
data for the pseudo-second-order model (Ahmad and Mirza, 2015; temperature. The negative value of ΔG0 for BG dye shows spontaneous
Khatoon et al., 2018). As the value of C is non zero proving adsorption nature of adsorption (Jayasantha Kumari et al., 2017). The positive and
involves a complex process and intraparticle diffusion is not the sole rate low ΔS0 (0.0726) showed increased randomness at the solid/liquid
determining steps. The plot of intraparticle diffusion model shows interface.
multilinearity of adsorbate adsorption, implying that two or more steps
occurring in adsorption process. The first linear portion is attributed to 3.6. Breakthrough study
external diffusion while second linear stage ascribed to the intraparticle
diffusion as a delayed process. The third linear portion shows the Breakthrough capacity and exhaustion capacity were the important
equilibrium establishment (Kumar et al., 2014a). parameter to access the economical feasibility of the process (Ahmad
and Mirza, 2017b; Khan Rao and Khatoon, 2016). Fig. 5b, represents
3.5. Thermodynamic study breakthrough curve which was obtained by plotting Ce/Co versus vol­
ume of effluent in (mL). The breakthrough curve indicated that 50 mL of
In the adsorption process, temperature plays an important role in the BG dye solution could be passed through the column without detecting
adsorption behaviour (Ahmad and Mirza, 2017a). Thermodynamic pa­ in the effluent. The breakthrough and exhaustive capacities were found
rameters such as standard free energy change (ΔG0) (kJ mol 1), to be 12.5 and 45 mg g 1, respectively.
enthalpy change (ΔH0) (kJ mol 1) and entropy change (ΔS0) (kJ mol 1
K 1) were obtained from the following relations. 3.7. Desorption and regeneration
0 0
ΔS ΔH
log Kc ¼ (13) The desorption result showed that above 84% of BG dye could be
2:303R 2:303RT
desorbed by 1M oxalic acid (CH2COOH)2 in first cycle without signifi­
ΔG0 ¼ RT ln Kc (14) cant loss in adsorption capacity. Regeneration plot (Fig. S7), represents
that as the no. of cycles increases, the % desorption decreases and it goes
where the slope and intercept of the linear plot of log Kc versus 1/T as up to 39% in fifth cycle with slight decrease in adsorption capacity. The
shown in Fig. 5a gives the value of ΔH0and ΔS0, T (K) is the absolute desorption of BG dye in (CH2COOH)2 indicate the involvement of
temperature, R (JK 1 mol 1) gas constant. physical forces in adsorption process, affirming thermodynamic result
Equilibrium constant Kc was calculated from the expression: (Ahmad and Mirza, 2018a). Therefore, the adsorbent can be reused up to
fifth cycle successfully. This showed the feasibility and cost-effective
C Ac viability of CTLISP and also reported elsewhere (Ahmad and Mirza,
Kc ¼ (15)
Ce 2018b). The excellent regenerative capability indicates that the present
low-cost adsorbent (CTLISP) has been proved to be the promising
where, CAc and Ce are the equilibrium concentrations of BG dye on
adsorbent in treatment of toxic BG dye from aqueous solution.
adsorbent and in solution, respectively.
The values of thermodynamic parameters were tabulated in Table 4.
The positive value of ΔH0 and ΔS0 for BG dye indicates that the 3.8. Specific surface area
adsorption of BG on the surface of CTLISP was endothermic with
increased in randomness at solid/liquid interface during adsorption Monolayer coverage of surface of CTLISP by BG dye can be used for
(Ahmad and Kumar, 2010; Ghasemi et al., 2014). The adsorption phe­ calculation of specific surface area using following equation:
nomena can be categorized as physisorption or chemisorption depend­ qm NA
ing on enthalpy change (ΔH0). If ΔH0 is less than 40 kJ mol 1, then the Specific surface area ðSSAÞ ¼ (16)
M
process is said to be physical in nature (Khatoon et al., 2018). In the
where, qm is the maximum monolayer coverage dye in (gg 1) of
Table 3 adsorbent, N is the Avogadro number, A is area per molecule on the
Kinetics parameters for the adsorption of BG dye on CTLISP. surface and M is the molecular weight of dye. Under the condition of
optimum flocculation, the area adsorbed by per molecule of BG dye is
Model Parameters Concentration (mg L 1)
taken as 92.1 Ao2, which corresponds to the molecule lying flat on the
25 50 100 adsorbent surface. The maximum specific surface area for BG dye by
Pseudo First Order qe (exp) (mg g 1) 2.486 4.884 8.832 using equation (16) was found to be 40.17 (m2 g 1) of adsorbent.
qe (cal) (mg g 1) 0.078 1.056 2.630
k1 (min 1) 0.018 0.013 0014
R2 0.938 0.925 0.950 3.9. Comparison with other adsorbents
SD 0.100 0.078 0.069
Pseudo Second order qe (exp) (mg g 1) 2.486 4.884 8.832 A comparison of monolayer adsorption capacities of various adsor­
qe (cal) (mg g 1) 2.487 4.901 8.849 bent with present work has been listed in Table 5. The table itself reveals
k2 (g mg 1 min 1) 1.044 0.052 0.020
R2 0.998 0.998 0.998
that the present adsorbent shows a high adsorption capacity towards BG
SD 0.130 0.631 0.348 dye as compare to other adsorbents. This suggests that the CTLISP ma­
Intra-particle diffusion Kid (mg g 1 min 1/2) 0.007 0.090 0.237 terial has great prospective in practical applications for the enhanced
C 2.397 3.678 5.771 removal of BG dye from aqueous solution and industrial waste water.
R2 0.915 0.938 0.970
SD 0.010 0.104 0.189
Elovich A (mg g 1 min 1) 2.365 3.314 4.779 3.10. Adsorption mechanism
B (g mg 1) 0.023 0.281 0.749
R2 0.960 0.910 0.964 To comprehend the mechanism of the interaction between func­
SD 0.007 0.127 0.211
tionalized CTLISP and molecules of BG dye, a number of different

6
R. Ahmad and K. Ansari Groundwater for Sustainable Development 11 (2020) 100417

Fig. 4. Adsorption kinetics (a) Pseudo-first order (b) Pseudo-second order (c) Intra-particle diffusion (d) Elovich for the adsorption of BG onto CTLISP (conditions;
pH ¼ 6; adsorbent ¼ 0.2 g; temperature ¼ 30 � C).

1
Fig. 5. Adsorption thermodynamics (a) and Breakthrough curve (b) for the adsorption of BG onto CTLISP (conditions; BG ¼ 50 mgL ; pH ¼ 6; adsorbent ¼ 0.2 g;
temperature ¼ 293–313 K; flow rate ¼ 1 mL min 1).

between positively charged cationic dye ions and lone pairs of the –OH
Table 4 and –COOH groups of CTLISP. The Dubinin–Radushkevich isotherm
Thermodynamic parameters for the adsorption of BG dye on CTLISP at different
results show that the mechanism of adsorption with respect to Gaussian
temperatures.
energy distribution onto a heterogeneous surface and determined based
Temperature KC ΔH0 (KJ ΔG0 (KJ ΔS0 (KJ mol 1
on the free mean sorption energy physical adsorption occurs on the
(0C) mol 1) mol 1) K 1)
surface of CTLISP. After the adsorption of BG dye, some changes in the
30 104.26 11.70 absorption wave numbers and also the intensities of absorption bands of
40 115.28 12.35
the adsorbent were observed. Indeed, slight shifts in the peak positions
50 133.77 10.34 13.15 0.073
were observed in the regions 3395–3401 and 1616–1652 cm 1 which
are probably due to the removal of BG over CTLISP via a strong
spectroscopic techniques such as FTIR, EDX, and X-ray diffraction were hydrogen bonds and electrostatic interactions between ions of the dye
used. The interaction between adsorbate–adsorbent depends on the molecules with the –NH2 and –OH groups of CTLISP.
chemistry of adsorbate, solution pH, chemical and physical nature of
adsorbent. At lower pH, the –OH and –COOH functional groups of 4. Conclusion
negatively charged adsorbent CTLISP have a strong coordinative affinity
towards BG dye by surface complexation through electrostatic interac­ Eco-friendly, cost-effective and novel LISP low-cost adsorbent was
tion while this affinity decreases at higher pH as due to repulsive force treated, characterized and explored for the removal of BG dye from

7
R. Ahmad and K. Ansari Groundwater for Sustainable Development 11 (2020) 100417

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