Surfaces and Interfaces 20 (2020) 100510

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Surfaces and Interfaces

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Efficient adsorbent derived from Haloxylon recurvum plant for the adsorption T
of acid brown dye: Kinetics, isotherm and thermodynamic optimization
⁎
Warda Hassana,b, Sajida Noureenb, Mujahid Mustaqeemb,e, Tawfik A. Salehc, , Shagufta Zafard
a
Department of chemistry, The Women University, Multan, Multan (60000), Pakistan
b
Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur (63100), Pakistan
c
Department of Chemistry, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
d
Department of Chemistry, Govt. Sadiq college women university, Bahawalpur (63100), Pakistan
e
Department of chemistry, Govt. Sadiq Egerton College Bahawalpur, 63100, Pakistan

A R T I C LE I N FO A B S T R A C T

Keywords: The capacities, mechanisms, and potential of low-cost Haloxylon recurvum stem (HRS) biomass for sorption of
Haloxylon recurvum acid brown 354 dye (AB354) from waters were studied. Fourier transformed infrared spectroscope (FTIR),
Acid brown scanning electron microscope (SEM), thermal analysis (TGA) and elemental analyzers were utilized for the
Kinetics characterization of biomass before and after sorption of dye. There was an enhancement in adsorption capacity
Isotherm
with increasing the dye concentrations. With an increase in the initial dye concentration, the increase in the
Cleaner production
sorption capacity of the biomass was noticed (i.e. 2.846 mg/g – 10.011 mg/g). The extent of removal of dye
decreased with the increase in temperature (i.e. 77.7% to 52.9%) and the particle size of the biomass (i.e. 81.3%
to 36.6%). Ho's pseudo-second-order kinetic model (χ2 = 0.0679361), as well as Langmuir
(χ2 = 1.05637 × 10–12) and Temkin sorption isotherms (χ2 = 1.36752 × 10–12), were well in line with the
sorption data and best represented the equilibrium sorption of the dye. Negative Gibb's free energy value ΔG
(-3.616–-0.333) and enthalpy ΔHo (-24.826) values were the indication of spontaneous, as well as feasible and
exothermic nature of the sorption process. The investigations demonstrated that HRS biomass was an attractive
and potential material for removal of acidic dye from dyed effluents than many others reported in the literature.

1. Introduction
Among the organic industrial water contaminant, dyes are an im-
portant class of pollutants [1]. About 12 to 14 % of these dyes are being
discharged to water bodies in the textile effluents. These dyes are highly
toxic to the human as well as aquatic life. In these wastewaters, these
dyes remain for a long time and cannot be removed without further
treatment [2]. Removal of these toxic dyes from water is a good means
to avoid their lethal effects. Decontamination of this dyed wastewater is
highly required for the betterment of human life [3,4]. Different
structural forms of these cationic, nonionic and anionic dyes exist. The
anionic (acid) dyes are more problematic as these dyes pass unaffected
through the conventional system. Anionic dyes are usually sodium salts
of sulfonic acids, having good solubility in water [5]. These are bril-
liantly colored, reactive and consist of ionizable acidic groups e.g.
sulfonates, carboxylates, and sulfates that are greatly attracted to
polyamide and protein fabrics. Therefore, these dyes are used to dye
silk, polyamide fibers, modified acrylics, and woolen textile. They not
only able to attach on the surface of other materials, but also give
colour to this substance and are resistant to detergents, etc. [6]. These
dyes involve aromatic structures due to which these are more resistant
to heat, light, and many other oxidizing agents [7]. It becomes difficult
to degrade them after they enter the water channel, owing to the syn-
thetic structures. In these wastewaters, these dyes remain for a long
time and cannot be removed without further treatment [8]. Removal of
these toxic dyes from water is a good means to avoid their lethal effects
[9].
Most of the cellulosic materials have negatively charged char-
acteristics, which is problematic for the sorption of acidic dyes from
their aqueous solutions [10]. Therefore an attempt was made to gen-
erate a system for the better sorption of the dye. For the last few years,
several natural materials are being used for the purpose [11]. These
natural materials also include biosorbents [12]. For removing dyes from
water bodies the use of biosorbents has been found highly effective due
to their economical, abundant and eco-friendly nature. A little litera-
ture is available about the sorption of acidic dyes by desert plants-based

⁎
Corresponding author.
E-mail address: tawfik@kfupm.edu.sa (T.A. Saleh).

https://doi.org/10.1016/j.surfin.2020.100510
Received 2 February 2020; Received in revised form 13 March 2020; Accepted 16 March 2020
Available online 17 March 2020
2468-0230/ © 2020 Elsevier B.V. All rights reserved.
W. Hassan, et al. Surfaces and Interfaces 20 (2020) 100510

biosorbents. The biomasses of various abundantly available desert

plants are also there to be explored for sorption of dyes. Haloxylon re-
curvum is the commonly found halophytic types of the desert plant, that
is abundantly available in cholistan desert areas of Bahawalpur, Paki-
stan [13]. This plant exists in the form of diffused shrub, having a
branched structure, and is almost leafless. It is 25–60 cm tall having
woody stems that exist in desert parts of Pakistan. The plant in-
florescences consist of short cups, 3–6 cm in form of long, scattered
spikes that are pale greenish in color [14]. It is also widely available in
different areas of the world and also contains a large number of binding
sites on its surface, which are potentially responsible for sorption of
pollutants from water [5,6,15]. Although much work has been pub-
lished on sorption studies of dyes using low-cost biosorbents still there
is a little literature available on the full study of comparison between
different sorbents used for the removal of acidic dyes. Consequently,
efforts are needed to study more materials for the removal of dyes.
This investigation puts an attempt to utilize this desert plant stems
to remove Acid Brow 354 (AB354) dye from the textile wastewaters.
Therefore the study aimed to conclude the adsorption capacity of this
commonly found desert plant for the sorption of acidic dye, to en-
courage the examination with different biosorbents e.g. fibers [16],
rubber leaf powder [17], shrimp shell [18] etc. used for the sorption of
acidic dyes. Also, kinetic and sorption equilibrium parameters for the
sorption of the selected biosorbent will be a good contribution to the
scientific basis to the traditional utilization of the plant as biosorbent.

2. Materials &methods
All the reagents and chemicals utilized were Merck (Germany),
analytical grade, and were utilized without purification. Haloxylon re-
curvum plant was gathered from Cholistan Desert area from district
Bahawalpur, the Pakistani area. The adsorbent was derived from H.
recurvumplant stems. The stems were cut and washed with tap water
and then dried. It was then ground and sieved into mesh size of
100.0 μm. It was then soaked in waters for 48 hr to separate any soluble
chemicals, then filtered and dried. Acid Brown 354 (AB354), a double
azo compound [C.I. 20177], is acidic in nature having chemical formula
C30H20N8Na2O12S2 and molecular weight 794.64 g/mol. It is a red light
brown colour dye used for dyeing wool, printing, and leather shading.
(Fig. 1).
2.1. Characterization of powdered biomass
The biosorbent material was characterized by different standard
techniques. Fourier Transformed Infrared (FTIR) spectrum was scanned
in the region 4000–400 cm−1using carry 630 Agilent via ATR mode.
Scanning Electron Micrograph (SEM) was obtained using Hitachi S-
4700 electron micrograph. Elemental analyzer Haloxylon recurvum-
stems (HRS) was determined by a “Vario EL III Elementar”.
2.2. Batch adsorption
The batch sorption studies were performed and different para-
meters, affecting the sorption process were examined. In a typical ex-
periment, a dye solution of known concentration (C0 = 25 mg/L,
40 mL) and amount (100 mg) of HRS biomass was taken at a particular
pH of the solution. The sample was then agitated (400 rpm) for a
specific period (5–180 min), withdrawn and centrifuged (EBA 20
Hettich). The supernatant was then analyzed for dye (Ce mg/L) at the
specific λmax for the dye solution (420 nm) by UV−Vis (Sp 50
Gallenkamp). The dye (qe, mg/g) sorbed per unit mass of dry HRS
biomass was computed by Eq (1) [19].
C0 − Ce
q (qe ) = ×V
m (1)
Where, q or qe (mg/g) is the amount of dye adsorbed, V (mL) = volume
Fig. 1. Haloxylon recurvm plant and Chemical formula of Acid brown 354 dye.
used and m (mg) = adsorbent used.
Time of contact was recorded from 5–180 min time range, pH from
2–9, concentration from 10 mg/L to 60 mg/L and dose from 0.05 g/L to
1 g/L and temperature from 298–343Krange. Prior to the measure-
ments, the wavelength of maximum absorption (λmax) of the dye was
detected. Also, the calibration plot was drawn by standard AB354 dye
solutions. All of the experimental results were the average values of
triplicate. Regression and Chi square (χ2) analysis were performed for
suitability of certain mathematical models.
For kinetic modeling, non–linear, Lagergren's model (Eq. 2), Ho's
model (Eq. 3) models were studied to the obtained experimental data
for insight learning of kinetics process. The Lagergren's pseudo-first-
order equation is the first-rate equation for the sorption of ad-
sorbate–adsorbent system based on solid capacity [20]. The model is
based on the fact that the rate of adsorption is related to available
sorptive sites, particularly suitable for low concentrations [17].
The non–linear form of Lagergren model is.
(
qt = qe 1 − e−k1 t ) (2)
The pseudo-second-order kinetic model shows sorption rate is di-
rectly related to the square of the number of binding sites available on
the adsorbent. The model has been derived from sorption processes in
which there is an exchange reaction that is the rate-controlling step
[21]. The non–linear form of Ho's model is
k2 qe2 t
qt =
1 + k2 qe t (3)
Rate determining step was found by using linear forms of
Intraparticle and liquid film diffusion models. Intraparticle diffusion
(IPD) model, is an empirical relationship in the sorption process where
uptake of solute is proportional to t1/2 instead of contact time.
qt = kip t 1/2 + Cip (4)
The diffusion model controls the adsorbate molecule migration from
the solution to the boundary layer of the solid phase.

2
W. Hassan, et al.
Bt = −kfd t + Cfd (5)
Where
Bt = ln(1 − qe / qt ) (6)
The Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-
R) sorption models were used to explain the sorption data. The non-
linear form of Langmuir Eq is
qm KL Ce
qe =
1 + KL Ce (7)
The RL separation factor indicates, the sorption process as un-
favorable (RL>1); favorable if 0 < R L < 1, linear if RL = 1; irrever-
sible if RL = 0, [22]. It is determined as
1 was 2.5 nm (2500 μm). The diameter of the dye was smaller than that of
RL =
1 + KL C0 (8)
The Freundlich isotherm considers that the sorption takes place on
the heterogeneous adsorbent with unequal distribution of energy.
Furthermore, the sorption capacity of adsorbent relates to dyes con-
centration. The nonlinear form of Freundlich Eq is
qe = KF Ce1/ n (9)
KF (mol/g) is the Freundlich constant. KF, roughly gives the idea of the
sorption capacity. Freundlich parameter “n” is the sorption intensity
that relates to the surface heterogeneity, the “n” value closer to zero is
the indication of a more heterogeneous surface of the adsorbent. The
value of n > 1, indicates favor of sorption process [23].
The Temkin isotherm gives the idea of the sorption energy i.e. the
sorption energy decreases as the degree of completion of sorption
centers of adsorbent increases. As the adsorbent–adsorbate interaction
increase, the heat of adsorption would decrease all of the molecules.
The Temkin isotherm is,
RT
qe = ln(a. Ce )
b (10)
Where “b” is Temkin constant; that relates to the heat of sorption (J/
mol); T is the temperature in K. The nonlinear form of the D-R model is
qe = qDR exp[β . (RT ln(1 + 1/Ce ))2 ] (11)
3. Results and discussion
3.1. Biomass characterization
FTIR is a good tool to prove the active sites present in the adsorbent.
The intensities and group frequencies of important FTIR peaks of
powdered biomass (Fig. 2a) confirmed the biosorbent heterogeneity
w.r.t functional groups. The FTIR analysis gave the proof of the pre-
sence of different characteristic functional groups, especially, hydroxyl
(3383.70 cm−1), carboxylic (1318.72 cm−1), carbonyl
(1738.84 cm−1), sulfate (1239.09 cm−1) and sugar derivative
(1031–1000 cm−1) groups [24, 25] on the surface of biosorbents,
Table 1. The –NH band was suspected to be underneath the broad peak
centred at 2918.77 cm−1. A variety of the functional groups that be-
have as binding sites are present on the surface of HRS biomass in-
dicated that the material might present several available sites for po-
tential attachment of AB354 dye molecules [15].
Fig. 2a also represents the FTIR spectrum of HRS biomass after
sorption of AB354 dye. For this purpose In 50 mg/L solution of dye 1 g
of biomass was added and the system stayed overnight. It was then
filtered and dye loaded biosorbent was characterized. It was observed
that there were small shifts in the position of FTIR peaks in dye loaded
biomass i.e from 3363 cm−1 in dye unloaded biomass to 3374 cm−1 in
dye loaded biomass. Some new peaks observed in dye loaded biomass at
2961.94 cm−1, 1422.70 cm−1 that indicated the presence of hydroxyl,
3
Surfaces and Interfaces 20 (2020) 100510
and C–H bonding, possibly present in dye molecule. The carbonyl peak
shifted from 1738.84 cm−1 to 1720.97 cm−1 after sorption of dye. The
appearance of a peak at 1509 cm−1 after sorption of AB354 dye in-
dicated the presence of NO2 group present in the dye. Similarly, the
strong band at 1022 cm−1 in the spectrum might be due to stretching
vibrations of S]O or C–N stretching vibrations of the amine group of
the sorbed dye. The very small shifts indicated the physical attachment
of dye molecule on the surface of biomass [26].
The SEM image of the pure biomass clearly showed the porous
structure of biosorbent which revealed that the surface of biomass was
asymmetrical and had significant numbers of pores and cavities which
provided a large surface area for the sorption of dyes molecule [27].
The calculated pores size at different magnifications, in HRS biomass
were 1.651 μm and 2.865 μm. The estimated diameter of AB354 dye
the calculated pore size diameter of the biosorbent. It was the indica-
tion that the dye might be adsorbed through diffusion into pores of the
biosorbent. Less number of pores observed on the surface of the bio-
sorbent after the sorption of dye which might be due to either accu-
mulation of dye on the surface biomass used. The SEM of the biomass
has been shown in Fig. 2b & c.
The analysis of the biomass showed different constituents e.g.
carbon (43.07%) nitrogen (2.104%) sulphur (0.13%) and hydrogen
(6.090%). The low nitrogen contents (2.104%) indicated the presence
of low protein contents. This was advantageous over protein-rich ad-
sorbents used, as protein-rich adsorbents putrefy in moist conditions.
It is necessary to understand the thermal decomposition of biomass
to determine the thermal stability of the biomass [8,28]. The curves of
TGA of the biomass sample was studied within the temperature range
10 °C–1000 °C with a temperature rising rate of 10 °C/min (Fig. 3).
These obtained TGA curves showed the thermal stability of biomass i.e
the biomass was stable even at high temperature range The curves
showed that biomass contained several carbon compounds e.g. carbon,
cellulose, lignin, and hemicellulose materials [29]. The organic com-
ponents might be responsible for the sorption of dyes.
3.2. Performance evaluation
3.2.1. Kinetic modeling
The equilibrium provides information about the time required for
significant sorption of dye on the adsorbent, after which no further
sorption process takes place. Sorption behavior of AB354 dye on the
selected biomass as a factor of time has been shown in Fig. 4a. Rapid
sorption rate was observed over the first 20 min (rapid sorption region).
After 20 min this fast sorption period was followed by a slow removal.
This slower uptake of the dye by the biomass has been shown in the
form of a curve in the plot (transition region). After 50 min, equilibrium
reached and the time curve became parallel to the x-axis, since no
further detectable sorption was observed (plateau region). Thus within
50 min, the sorption process reached equilibrium and the biomass at-
tained saturation understudied conditions. The slower uptake of dye at
later stages was due to a lower number of active sites [20].
The sorption kinetics studies give an idea about the mechanism and
the rate of sorption process is important in controlling the removal of
contaminants [30]. The non–linear plot of Lagergren and Ho's models
has been shown in Fig. 4b. The values have been shown in Table 2. The
less χ2 value as well as qe(cal) (mg/g) values from pseudo-second-order
plot fit well the tests results, indicating that this model was applicable
to experimental data i.e. qe(cal) = 610.14 ± 0.296 mg/g which was
comparable to the data i.e. qe(exp) (6.869 mg/g).
In Intraparticle diffusion model, qt versus t1/2plot would be a
straight line with Cip equal to zero if IPD is the only operative me-
chanism. If there is some value of intercept i.e. the plot does not pass
through the origin, then sorption is mainly by diffusion model [31]. The
plot for IPD (Fig. 4c) was found to be linear for the studied set of data
indicated that intraparticle diffusion was there. The value of kip was
W. Hassan, et al. Surfaces and Interfaces 20 (2020) 100510

Fig. 2. FTIR spectrum of Haloxylon recurvum biomass a), before and after sorption b) SEM of biomass before sorption. c) after sorption.

Table 1
List of functional groups on the prepared biosorbents.
Functional groups Frequencies of different groups

HRS Hydroxyl group 3383.70 cm−1

Carboxylic group 1318.72 cm−1
Carbonyl group 1738.84 cm−1
Sulphate group 1239.09 cm−1
Sugar's Derivatives 1031–1000 cm−1
Amino groups 2918.77 cm−1
HRS-AB354 Hydroxyl group 2961.94 cm−1
C-H bond 1422.70 cm−1
Shifting of carbonyl peaks 1720.97 cm−1
Nitro group 1509 cm−1
Sulphr group 1022 cm−1
Fig. 3. Thermal Analysis of HRS Biomass.

obtained from plot Fig. 4.

In the liquid film diffusion model, Bt vs t, the plot would be a
straight line with Cfd equal to zero if it is the only operative mechanism.
In case if the lines do not pass into the origin, the liquid diffusion model
is the only operative mechanism i.e. rate-limiting process can be by film
diffusion. However, if there is some value of intercept then adsorption
kinetics may be controlled by some other mechanism e.g. IPD [32]. The
values of kfd were obtained from line slope. The non-zero value of the
intercept (Cfd) indicated that boundary layer diffusion (Fig. 4d) was
also playing an important role in the rate-determining step. Such results
were also similar to the sorption studies of dyes onto other sorbents as
reported in the previous studies [23,33].
3.2.2. Equilibrium modeling
The amount of dye sorbed on the biosorbent was observed to be
increased with changing/increasing the concentrations of dye (Fig. 5a).
The adsorption capacity was increased by changing the concentration
which can be due to high molecules of dye being attached to available
sites at HRS [34,35].
The sorption equilibrium which determines the sorption capacity of
the sorbent is an important factor to design the better sorption system.
Such equilibrium relationships are described by sorption isotherms

4
W. Hassan, et al.
Fig. 4. (a) Impact of time of contact on the removal of AB354 by HRS biomass;
(b) Non–linear Pseudo first order & second-order kinetics; (c) Intraparticle
diffusion model; (d) Liquid Film diffusion model.
[36]. For the purpose, the most important and studied models (Lang-
muir, Freundlich, Temkin, and D-R) were studied. Nonlinear modelling
was adopted. Igor® software was used to find the best fit of isotherms
with experimental results. The software was based on the “trial and
5
Surfaces and Interfaces 20 (2020) 100510
error” method. To assess the ability of different isotherm models for
correlation with experiments. (Fig. 5b).The graph was plotted between
the dye sorbed per unit mass of sorbent, qe, against the remaining
concentrations of dye, Ce (mol/L). The comparison of the chi square
(χ2) values for these isotherms has been made and has been depicted in
Table 3. The smaller chi square value indicates the better fit of the
model with the experiments. The Langmuir and Temkin isotherm
models fit experimental data as compared to the Freundlich and D–R
model (Fig. 5b).
3.2.3. pH effect
The pH of the dye-containing wastewater varies. The sorbate–sor-
bent interaction is highly exaggerated by the pH of the solutions due to
the reason that the dyes have different functional groups and un-
saturated bonds. Due to the presence of the functional sites, these dyes
have changed ionization potential at different pH values. The aqueous
chemistry as well as the surface binding-sites on the adsorbent, both
impacted with changing pH. With changing solution pH, the nature of
active sites, on the surface of the biomass changes. For example: in a
highly acidic pH range, the functional groups get protonated and be-
have like positively charged moieties [37]. Whereas at higher pH range
(basic region), deprotonation of these functional groups occurs thus
behaves as negatively charged moieties. As the pH is increased from
high acidic range to low acidic region, the positive behavior of the
biomass gets changed to the negative one [38,39].
The high removal of dye was observed at pH 2. The uptake of dye
was decreased when the pH of the dye solution was increased (Fig. 6a).
The sorption capacity of the biomass increase for acidic (anionic or
negatively charged) when the pH decreased in the tested range [36].
The very low optimum pH range for the maximum removal of dye is
related to the point of zero charge pH, pHpzc. In our studies, pHpzc of
HRS biomass was found to be 6.3 [15]. At a pH of less than 6.3, HRS
would be positively charged, which attract negatively charged dye
[40]. An increase in the solution pH caused the decrease in the surface
positive charge on HRS. This caused a decrease in the attraction be-
tween HRS and dye ions resulting, a decrease in qe(mg/g) value with
the increase in solution pH (Fig. 6a). This was under the results re-
ported in the literature, that acid dyes mostly adsorbed at highly acidic
pH values.
3.2.4. Temperature effect
Temperature is a key factor affecting the adsorption process in its
real application. The temperature effect on the dye sorption was studied
and has been depicted in Fig. 6b. The negative slope is the indication of
a decrease in the adsorption with high temperature (298K–343K)
within the conditions of the test. Actually, at high temperature, the
physical interactions between the dye molecules and the adsorbent
binding sites, weakened because the increase in K.E caused detachment
of dye molecule from that of the adsorbent. Furthermore, the solubility
of dyes increased with increasing temperature thus enhanced the in-
teractions forces of absorbents and adsorbates [41,42].
Based on fundamental thermodynamics concept, energy and en-
tropy factors is to determine spontaneity of the process. The thermo-
dynamic factors, (ΔGo, ΔHo and ΔSo), help understand the adsorption
mechanism [38].
The change in the standard Gibb's free energy (ΔGo, J/mol) was
determined as:
ΔGo = −RT ln kd (11a)
Where Kd [(Co –Ce)/Ce]is the equilibrium constant, T is absolute tem-
perature [36]. Van't Hoff Equation was used to define the values of
standard enthalpy change as well as standard entropy change [43].
ΔGo = ΔH o − T ΔS o (12a)
Plots of ΔG and T, give straight lines and the value of ΔS (J/mol K)
o o
and ΔHo (J/mol) were gained. The negative ΔGo value indicated
W. Hassan, et al. Surfaces and Interfaces 20 (2020) 100510

Table 2
Determined kinetic factors for sorption of acid brown 354 by HRS biomass.
Model Equation Parameters R2 χ2

Pseudo first order qt = qe(1 − e−kt) qe(cal) (mg/g) k1 (min−1) ____ 0.0878414
7.3811 ± 0.165 0.051848 ± 0.00259
Pseudo second order k 2 qe2t qe(cal) (mg/g) k2 (g mg−1 min−1) ____ 0.0679361
qt =
1 + k 2 qe t 10.14 ± 0.296 0.0042832 ± 0.000396
0.920 ± 0.090 0.435 ± 0.013
Intra particle diffusion qt = kipt1/2 + Cip kip (mg/g min1/2) Cip 0.9764 ____
1.072 ± 0.068 0.296 ± 0.336
Liquid film model Bt = −kfdt + Cfd Kfd Cfd 0.9469 ____
0.037 ± 0.004 0.114 ± 0.093
qe(exp) = 6.869mg/g

[45]. The value of ΔSo indicated random adsorbent–adsorbate interface

during the removal process [46] .The negative value of ΔSo(–71.651J/
molK) corresponds to a reduction in randomness [38].

4. Conclusion

The present work indicated that the locally available inferior quality
desert plant could be used as sorbents for the dye removal from waste
effluents. The findings of the work indicated the sorption capacity of
powdered HRS for acidic dye removal. FTIR analysis revealed the
available binding sites on the biomass proved to be preferred species on
the adsorbent surface for most sorption processes. SEM analysis ex-
hibited the highly porous surface having a large surface area of bio-
mass. The elemental analysis also confirmed the presence of different
percentages of elements. The biomass evaluated as a potential biosor-
bent, extremely dependent on the different parameters like time of
contact, concentration, temperature, and pH of the system. A very good
correlation of kinetic data obtained, with that of experimentally ob-
tained data that was the indication that the sorption process fit the
pseudo first-order model and intraparticle diffusion kinetic model.
There was a great interaction with in the first 50 min of contact times.
The adsorption results fit better to the Langmuir and Temkin model
indicated the physical sorption on the surfaces of biomass with energy
levels in uniform distribution. The sorption capacity of biomass was
connected to the initial dye concentrations at the equilibrium period.
The negative values of Gibb's free energy (ΔGo, Enthalpy (ΔHo) showed
Fig. 5. (a) Effect of initial dye concentration (100 mg, 40 mL & 400rpm) (b) spontaneous exothermic adsorption. Negative entropy (ΔSo) indicates a
Nonlinear fitting of equilibrium models. reduction in randomness at the adsorbate-adsorbent interfaces as a
result of the sorption process. The present studies conclude that the
Table 3 Haloxylon recurvum plant stems, as economical and eco–friendly ad-
Determined equilibrium models for the sorption of acid brown 354 dye by HRS sorbent that could be employed as an alternative biomaterial to the
biomass. current expensive materials used for removal of dyes from the dye
bearing waters.
Model Parameters Values

Langmuir qmax (mg/g) 1.6692 × 10−5 ± 1.01 × 10−6 Author contribution

KL 79614 ± 1.32 × 10+4
RL 0.143-0.500
χ2 1.05637 × 10−12
Warda Hassan performed the experiments and results. Sajida
Freundlich KF (mol/g)1-1/n 0.00097485 ± 0.000699 Noureen performed the experiments and results. Mujahid Mustaqeem
n 2.3401 ± 0.37 performed the experiments and results. Tawfik A. Saleh reviewed the
χ2 3.93901 × 10−12 paper and checked the manuscript. Shagufta Zafar reviewed the paper
Temkin a 6.7785 × 105 ± 1.09 × 105
and checked the manuscript
b 6.3236 × 108 ± 3.14 × 107
χ2 1.36752 × 10−12
D-R qDR (mol/g) 9.805 × 10−4 ± 3.06 × 10−5 Declaration of Competing Interest
β (mol2/J2) 3.277 × 10−3 ± 4.56 × 10−4
E 12.352
χ2 3.122 × 10−12 There is no conflict of interest

Acknowledgement
spontaneous nature and confirmed the feasibility of the adsorption
process [44] (Fig. 6c). The value of ΔHo gave the idea about the route of We are thankful to The Women University Multan, Pakistan and The
energy in the system, Table 4. The negative value of ΔHo(–24.826 kJ/ Islamia University of Bahawalpur for providing necessary facilities for
mol)is an implication of the exothermic nature of the sorption process research work.

6
W. Hassan, et al. Surfaces and Interfaces 20 (2020) 100510

Fig. 6. (a) Effect of pH (C0 25mg/L, 100 mg, 40 mL); (b) temperature Effect on sorptive removal of AB354 by HRS. (c) Change in standard Gibb's free energy with
temperature for sorption of AB354 by HRS.

Table 4 [15] T.A. Saleh, Characterization, Determination and Elimination technologies for Sulfur
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