Chemosphere 190 (2018) 97e102

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Chromium (Ⅵ) removal from aqueous solutions through powdered

activated carbon countercurrent two-stage adsorption
Wenqiang Wang
College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China

h i g h l i g h t s

The PAC countercurrent two-stage adsorption process was performed.

The Cr(VI) removal efficiency was improved by > 50% by the process.

A calculation method correlating the effluent Cr(VI) concentration and PAC dose was feasible.

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

Article history: To exploit the adsorption capacity of commercial powdered activated carbon (PAC) and to improve the
Received 1 June 2017 efficiency of Cr(VI) removal from aqueous solutions, the adsorption of Cr(VI) by commercial PAC and the
Received in revised form countercurrent two-stage adsorption (CTA) process was investigated. Different adsorption kinetics
29 July 2017
models and isotherms were compared, and the pseudo-second-order model and the Langmuir and
Accepted 25 September 2017
Freundlich models fit the experimental data well. The Cr(VI) removal efficiency was >80% and was
Available online 28 September 2017
improved by 37% through the CTA process compared with the conventional single-stage adsorption
Handling Editor: Xiangru Zhang process when the initial Cr(VI) concentration was 50 mg/L with a PAC dose of 1.250 g/L and a pH of 3. A
calculation method for calculating the effluent Cr(VI) concentration and the PAC dose was developed for
Keywords: the CTA process, and the validity of the method was confirmed by a deviation of <5%.
Chromium © 2017 Published by Elsevier Ltd.
Powered activated carbon
Countercurrent two-stage adsorption

1. Introduction A variety of techniques have been developed to remove Cr(VI),

Cr(VI) is classified as a carcinogen by the International Agency
for Research on Cancer due to its strong mutagenic and teratogenic
properties (De Flora, 2000), and the US Environmental Protection
Agency has established 0.1 mg/L as the maximum total Cr con-
centration in drinking water (Costa, 2003). Currently, the wide-
spread use of Cr(VI) and its compounds in different industries, such
as mining operations, electroplating, leather tanning, water cool-
ing, power generation and petroleum refining, has led to numerous
diseases and serious environmental pollution (Cao et al., 2014). It
has been reported that long-term exposure to Cr(VI) ions increases
the risk of dermatitis; damage to the liver, kidney circulation, and
nerve tissue; and death (Kotas and Stasicka, 2000). Therefore, there
is a need to develop a more effective methodology to control the
discharge of Cr(VI) into the environment.
E-mail address: wwqzs@126.com.
including adsorption (Di Natale et al., 2015; Sun et al., 2015;
Demiral et al., 2008), precipitation (Gheju and Balcu, 2011; Golder
et al., 2011), membrane separation (Gherasim and Bourceanu,
2013; Bao et al., 2015) or solvent extraction (Wionczyk et al.,
2011) combined with adsorption and ion exchange on clays
(Bhattacharyya and Gupta, 2008), biomaterials (Zhu et al., 2016;
Albadarin et al., 2011; Mohan et al., 2011; Mohanty et al., 2006),
nanocomposites (Kara and Demirbel, 2012; Gu et al., 2012), ex-
change resins (Polowczyk et al., 2016; Kowalczyk et al., 2013), and
biological processes (Chen and Gu, 2005). Most of these techniques
have limitations such as high capital and operational costs, as well
as issues with the disposal of residual metal sludge (Sharma and
Forster, 1994). In contrast, adsorption technologies for Cr(VI)
removal have been investigated in both laboratory and industrial
settings due to the high adsorption capacities, operational conve-
nience, versatility, and range of the available compounds (Min et al.,
2015). Natural minerals (Swas and Uysal, 2014); artificial meso-
porous silica materials; various non-commercial, self-synthesized

https://doi.org/10.1016/j.chemosphere.2017.09.141
0045-6535/© 2017 Published by Elsevier Ltd.
98 W. Wang / Chemosphere 190 (2018) 97e102
polymer or copolymer adsorbents (Illanes et al., 2008; Sun et al.,
2013; Wang et al., 2015); many agricultural wastes; and different
modified activated carbons had been used as sorbents for Cr(VI)
adsorption from wastewater. However, the largest obstacle to the
use of these materials is their inability to meet commercial demand
due to high consumption. As a result, industries have depended on
commercial activated carbons (Anupam et al., 2011). Hence,
another way to reduce the cost of Cr(VI) removal from wastewater
through adsorption is to explore the adsorption capacity and
reduce the dose of these carbons.
It is commonly recognized that countercurrent adsorption can
improve the adsorption capacity of activated carbon, but powdered
activated carbon (PAC) cannot be used in a traditional column
countercurrent adsorption operation, which requires granular
activated carbon. However, when combining PAC adsorption with a
microfiltration (MF) membrane, countercurrent adsorption opera-
tion can be achieved. The effectiveness of a PAC countercurrent
multi-stage adsorption/MF hybrid process has been demonstrated
by the removal of organics from a reverse osmosis concentrate
(Zhao et al., 2012; Wang et al. (2013b); Wei et al., 2014).
The objective of this study was to explore the countercurrent
two-stage adsorption (CTA) process for the removal of Cr(VI) from
aqueous solutions using commercial PAC. At the same time, the
method for calculating the PAC dose and effluent Cr(VI) concen-
tration was determined and validated.
2. Materials and methods
2.1. Materials
The materials used for the experiments were potassium di-
chromate (K2Cr2O7), sulphuric acid, hydrochloric acid, phosphoric
acid, sodium hydroxide, and acetone obtained from Sinopharm
Chemical Reagent Co. (Shanghai, China) and sodium hydroxide
supplied by Hengxing Chemical Reagent Co. (Tianjin, China). The
commercial PAC (200 mesh) was purchased from the Luda Co.
(Zunhua, China), and more information about the PAC is described
in the literature (Zhao et al., 2012). Prior to use, the PAC was baked
in an oven at 105  C for 2 h to remove any moisture. All chemical
regents were of analytical grade, the Cr(VI) solution with an initial
concentration of 50 mg/L was prepared by dissolving potassium
dichromate with distilled water.
2.2. Batch adsorption experiment
The influences of contact time (0e90 min, at a pH of 4 and a
PAC dose of 1.0 g/L), initial pH (2.0e11.0, for a contact time of
30 min and a PAC dose of 1.0 g/L), and PAC dose (0.2e2.2 g/L, at a
pH of 3 and a contact time of 30 min) on Cr(VI) removal in a
batch mode of operation under constant conditions were recor-
ded (a shaker speed of 200 rpm, a temperature of 293 K and an
initial Cr(VI) concentration of 50 mg/L). The pH values of the
adsorbate solutions were controlled by adding 0.1 M hydro-
chloric acid or sodium hydroxide. Once equilibrium was attained,
the adsorbent was separated from the solution though a 0.45 mm
filter membrane, and the equilibrium concentration was deter-
mined at the wavelength for maximum adsorbance
(lmax ¼ 540 nm) by the 1,5-diphenyl carbazide method using a
UVevis spectrophotometer (752, Shanghai Jinghua Instruments
Co., China).
The amount of Cr(VI) per unit weight of adsorbent, qe (mg/g)
was calculated by the following equation:
VðC0  Ce Þ
qe ¼
W
where V (L) is the volume of Cr(VI) solution, C0 and Ce (mg/L) are
the initial and final concentrations of Cr(VI) in solution, respec-
tively, and W (g) is the weight of adsorbent. All results were re-
ported as the average values for duplicate experiments.
2.3. CTA experiments
The CTA experiments were batch processed using a magnetic
stirring pressure cup with an MF membrane disc; the adsorption
device is shown in Fig. S1. To ensure that the MF membrane was
immersed, a portion of the equilibrium effluent remained in the
pressure cup.
Fig. 1 shows a schematic of the CTA process. During the initiation
stage, the V ¼ 0.2 L Cr(VI) solution with an initial Cr(VI) concen-
tration of C0 ¼ 50 mg/L and a fresh PAC of 0.2 g corresponding to a
PAC dose of m=V ¼ 1.0 g/L were sequentially added into the pres-
sure cup for 30 min of adsorption while stirring at 293 K. Next,
0.8Vequilibrium effluent was discharged, and 0.2Veffluent
remained to ensure MF membrane immersion. Afterward, the
operational stage experiments were repeated.
During the operational stage, the 0.8VCr(VI) solution was added
into the pressure cup to form a mixture with the 0.2Veffluent
(Cr(VI) concentration of Ce2 ) remaining after the last effluent
cycle. The mixture, which had a Cr(VI) concentration of
=
C0 ¼ 0:2Ce2 þ 0:8C0 , stayed in contact with the loaded PAC
remaining in the pressure cup after the last effluent cycle for 30 min
to achieve a Cr(VI) concentration of Ce1 ; this was considered second
stage adsorption, during which, fresh PAC was not added. After the
second adsorption, the fresh PAC of m=V ¼ 1.0 g/L was added into
the pressure cup for 30 min of adsorption to further reduce the
Cr(VI) concentration from Ce1 to Ce2 ; this was considered first stage
adsorption. Ce2 was the final effluent Cr(VI) concentration of the
CTA process.
During the CTA process, the PAC experienced two-stage
adsorption, and its adsorption capacity was sufficiently explored.
For the same PAC dose, the CTA process can be expected to remove
more Cr(VI) than the conventional single-stage adsorption (CSA)
process. The average values for two parallel experiments were
reported.
3. Results and discussion
3.1. Adsorption kinetics
The adsorption kinetics provide valuable information regarding
the equilibrium time and the adsorption mechanism along with the
reaction pathways. Fig. 2 depicts the effluent Cr(VI) concentration
as a function of adsorption time; the effluent concentration of
Cr(VI) rapidly decreased at the initial stage with a high adsorption
rate due to the availability of large number of adsorption sites
which saturates with time and tended to remain almost constant
after an optimum adsorption time of 30 min. Therefore, the equi-
librium time for Cr(VI) removal was 30 min.
The pseudo-first-order kinetics is one of the most used models
to describe adsorption from aqueous solution by solid adsorbent.
The pseudo-second-order model based on the assumption that the
rate limiting step might be chemical adsorption involving valence
forces through sharing or exchange of electrons between adsorbate
and adsorbent. The intra-particle diffusion model is of major
concern because it is the rate-determining step in the liquidesolid
adsorption systems. During the batch mode of operation, there is a
possibility of transport of adsorbate species into the pores of
adsorbent, which is often a rate-controlling step. Table S1 displays
(1) the parameters calculated from the three models and the kinetic
 W. Wang / Chemosphere 190 (2018) 97e102
Fig. 1. Schematic diagram of the CTA process.
plots (Fig. S2). Conformity between experimental data and the
model-predicted values was expressed by the correlation coeffi-
cient (R2 ). A relatively high R2 value indicated that the model
successfully described the kinetics of Cr(VI) adsorption. Through
comparing R2 of these three models, it was determined that the
pseudo-second-order model fit the kinetics data better than the
other two models. The theoretical qe values calculated from the
first- and second-order kinetic models were 12.74 mg/g and
20.37 mg/g, respectively, and the calculated adsorption capacity
(qe;cal ) from the pseudo-second-order-kinetic model was very close
to the experimental adsorption capacity (qe;exp ) of 20.13 mg/g,
indicating that the adsorption process followed the pseudo-
second-order kinetic equation. This result also demonstrates that
the chemical process controls the adsorption of Cr(VI) onto the
commercial PAC, which occurs at high Cr(VI) concentrations and
when the interactions of the ions and the active sites on the surface
are effective. The intra-particle-diffusion model is always used to
comprehensively illustrate the adsorbate diffusion mechanism and
determine whether intra-particle-diffusion is the rate-limiting
factor controlling the adsorption process especially in a solid-
liquid adsorption system. R2 < 0.96 indicated that the intra-
particle-diffusion model was not the only rate-limiting step, and
a multi-step process is expected to work during the entire time
range. The large kP1 value of the intra-particle diffusion model
suggests that the commercial PAC initially adsorbed the Cr(VI)
though the external surface adsorption caused by capillary effect or
the rate-controlled intra-particle diffusion process at a high diffu-
sion rate, but the small kP2 value indicates that the final equilibrium
stage where intra-particle diffusion slows down due to limited
Fig. 2. Effect of adsorption time on Cr(VI) removal by commercial PAC (PAC
dose ¼ 1.0 g/L; pH ¼ 4; initial Cr(VI) concentration ¼ 50 mg/L; and
temperature ¼ 293 K).
99
adsorption sites and repulsive forces between the Cr(VI) ions on the
solid and bulk phases had a low diffusion rate.
3.2. Effects of solution pH on Cr(VI) adsorption
The pH of the aqueous solution is an important parameter for
the removal of heavy metals because it affects both the surface
charge of an adsorbent and the speciation of a heavy metal, so the
heavy metal adsorption process differs with the pH level (Liu et al.,
2012). The effluent Cr(VI) concentration, with an initial value of
50 mg/L, over a pH range of 2.0e11.0 is depicted in Fig. 3, it is clear
that the adsorption of Cr(VI) onto the commercial PAC is signifi-
cantly influenced by the solution pH and that the Cr(VI) concen-
tration decreases as pH decreases. There was a sharp decrease in
the effluent concentration of Cr(VI) when pH decreased from 5.0 to
2.0, but the effects were negligible over a pH range of 6.0e11.0.
Cr(VI) exists in three different ionic forms (HCrO 2
4 , Cr2O7 , and
CrO2
4 ), and the species ratio depends on the pH of the solution
system (Singh and Tiwari, 1997). In an acidic solution, Cr(VI) pre-
dominately exists as HCrO 2
4 and is transformed into CrO4 when
the pH increases. The concentration of Cr(VI) decreased in the
lower pH ranges due to a high electrostatic force of attraction. The
surfaces of the adsorbent were negatively charged at pH > pHpzc
(pzc-point of zero charge) and positively charged at pH < pHpzc
(Sun et al., 2014). At lower pH (pH < pHpzc), the surface of the
adsorbent was positively charged, and at the same time more Hþ
ions are neutralized by the negative charge on the adsorbent sur-
face. Due to the high electrostatic force of attraction between the
positively charged adsorbent and the negatively charged chromate
Fig. 3. Effect of pH on Cr(VI) removal by the commercial PAC (PAC dose ¼ 1.0 g/L;
initial Cr(VI) concentration ¼ 50 mg/L; and temperature ¼ 293 K).
100 W. Wang / Chemosphere 190 (2018) 97e102
ions, the diffusion of chromate ions into the bulk of the adsorbent
increases (Rao et al., 2002). In contrast, at alkaline pH ranges
(pH > pHpzc), the surface of the adsorbent was negatively charged,
and the electrostatic repulsion between the negatively charged
surface of the adsorbent and the negatively charged Cr(VI) ions, as
well as the competition between the Cr(VI) ions and OH ions in
the aqueous solution for the adsorption sites, reduced the removal
of Cr(VI) (Sun et al., 2014). The lowest concentration of Cr(VI)
occurred at a pH of 2.0, but there was only a minute decrease in the
concentration of Cr(VI) from pH 3.0 to pH 2.0. Therefore, a pH of 3.0
was considered the optimal value for further studies of Cr(VI)
adsorption on the commercial PAC.
3.3. Adsorption isotherms
Isotherms for the adsorption of Cr(VI) onto the commercial PAC
showed how Cr(VI) interacted with carbon as well as the rela-
tionship between the amounts of adsorbed Cr(VI) (qe ) and its
equilibrium concentration (Ce ) in solution; these parameters were
significant for the application of adsorbents. Three commonly used
isotherm models, the Langmuir, Freundlich, and Temkin isotherms,
were applied for the data analysis. The Langmuir model assumes
that the adsorption of adsorbate molecules occurs on a homoge-
neous surface by monolayer adsorption without any interaction
between the adsorbed molecules (Deng et al., 2009). The Freund-
lich model is widely applied in multi-layer sorption caused by the
presence of different functional groups on heterogeneous surfaces,
and it incorporates various adsorbent-adsorbate interactions to
describe the non-ideal and reversible adsorption (Deng et al.,
2009). Finally, the Temkin model describes the uniform distribu-
tion of binding energies, and the adsorption heat of all the mole-
cules in the layer decreases linearly rather than logarithmically
with coverage (Foo and Hameed, 2010).
The calculated parameters of the models by the isotherms plots
(Fig. S3) are presented in Table 1. For the commercial PAC, the
correlation coefficients fit by the Freundlich and Langmuir iso-
therms were higher than those fit by the Temkin isotherm, and the
correlation coefficient for the Freundlich isotherm was slightly
higher than that for the Langmuir isotherm. Similar results were
also reported by Sun (Sun et al., 2014). It is also evident from the
correlation coefficient values that the Freundlich isotherm fitted
the experimental data particularly well, which indicates the het-
erogeneous carbon surface and the multi-layer coverage of Cr(VI). A
value of n larger than 1 indicates that Cr(VI) is favourably adsorbed
by the commercial PAC. The maximum adsorption capacity (qm )
value, as calculated from the Langmuir adsorption isotherm for
Cr(VI), was 43.29 mg/g, which was also considerably higher than
the maximum adsorption capacity of most reported adsorbents for
a given pH (Table 2). It appeared that the commercial PAC has
desirable qualities for the removal of Cr(VI).
Table 1
Adsorption isotherm model constants for Cr(VI) adsorption onto the commercial
PAC (initial Cr(VI) concentration ¼ 50 mg/L; temperature ¼ 293 K; pH ¼ 3; and
adsorption time ¼ 30 min).
Isotherms Parameters Values
Langmuir qm (mg/g) 43.29
kL (L/mg) 0.0617
R2 0.9774
Freundlich kF (mg/g (l/mg)1/n) 7.237
n 2.523
R2 0.9779
Temkin kT (L/mg) 0.5475
B 9.997
R2 0.9622
3.4. CTA process
3.4.1. Calculation method
A calculation method to predict the effluent Cr(VI) concentra-
tion according to the PAC dose of the CTA process was developed
based on the adsorption isotherm equation and the accumulative
adsorption principle (Zhang et al., 2009). If PAC desorption did not
occur, then the adsorption capacity would be cumulative in
accordance with the isotherm equation. The multi-stage adsorption
capacity of PAC can be calculated appropriately using Eq. (2).
C0  Cej
qej ¼ qeðj1Þ þ ð j > 1Þ (2)
m=V
where qej and qeðj1Þ are the PAC adsorption capacity for j stages and
j  1 stages (mg/g), respectively; C0 and Cej are the initial and
equilibrium adsorbate concentration (mg/L); m=V is the PAC dosage
(g/L). In addition, the variations in isotherm parameters due to the
different initial adsorbate concentrations were ignored to simplify
the calculation (Zhao et al., 2012). The adsorption isotherm equa-
tions obtained with the initial Cr(VI) concentration of C0 were used
to calculate the equilibrium Cr(VI) concentration with the initial
=
Cr(VI) concentration of C0 or Ce1.
As shown in Fig. 1 for first stage adsorption, when 1.0 g/L fresh
PAC was added into the pressure cup to adsorb Cr(VI) for 30 min,
the Cr(VI) concentration was reduced from Ce1 to Ce2 . According to
the Freundlich equation and the parameters (Table 1), Eq. (3) was
obtained:
1=n Ce1  Ce2 1=2:523
qe ¼ kF Ce ¼ ¼ 7:237Ce2 (3)
1:0
For second stage adsorption, the remaining adsorption capacity
of the loaded PAC after first stage adsorption during the last effluent
=
cycle reduced the concentration of Cr(VI) from C0 ¼ 0:2Ce2 þ 0:8C0
to Ce1 . The surplus adsorption capacities of the dual-loaded PAC
were ignored when compared to the fresh PAC. Therefore, the total
adsorption capacity of the PAC at a dose of m=V ¼ 1.0 g/L for the CTA
process was calculated by Eq. (4), which was deduced from
Freundlich equation and Eq. (2) following the accumulative
adsorption principle (Zhang et al., 2009).
0:2Ce2 þ 0:8C0  Ce1 Ce1  Ce2 1=2:523
þ ¼ 7:237Ce1 (4)
1:0 1:0
Eq. (4) describes the CTA process of the operational stage. The
second item on the left-hand side of Eq. (4) represents fresh PAC
adsorbing low-concentration Cr(VI), and the first item represents
loaded PAC adsorbing high-concentration Cr(VI). By solving Eqs. (3)
and (4), the values of Ce1 and Ce2 were 29.14 mg/L and 10.65 mg/L,
respectively.
Similarly, the calculation method could be based on the Lang-
muir equation and Eq. (2) as shown by Eqs. (5) and (6):
Ce1  Ce2 0:0617  43:29Ce2
¼ (5)
1:0 1 þ 0:0617Ce2
0:2Ce2 þ 0:8C0  Ce1 Ce1  Ce2 0:0617  43:29Ce1
þ ¼ (6)
1:0 1:0 1 þ 0:0617Ce1
By solving Eqs. (5) and (6), the values of Ce1 and Ce2 were
28.08 mg/L and 10.79 mg/L, respectively.
3.4.2. Validation of the calculation method
The effluent Cr(VI) concentration could be calculated using the
Freundlich or Langmuir equations for the CSA process and by the
 W. Wang / Chemosphere 190 (2018) 97e102 101

Table 2
Comparison of maximum Cr(VI) adsorption capacity (qm ) with various adsorbents.

Adsorbents Initial concentrations (mg/L) pH qm (mg/g) References

AC derived from olive bagasse 50e500 2.0 88.59 Demiral et al. (2008)
AC-Fe 5.7e63.3 5.38 34.39 Sun et al. (2014)
Coconut shell carbon 5e25 4.0 10.88 Babel and Kurniawan (2004)
AC derived from waste sawdust 100 4.0 13.85 Malwade et al. (2016)
Agricultural waste-based AC 20e60 1.5 38.5 Chaudhuri and Khairi Bin Azizan (2012)
PAC 250-50,000 4.0 46.9 Jung et al. (2013)
AC prepared from peanut shell 10e100 4.0 16.26 AL-Othman et al. (2012)
AC prepared from crofton weed 100 3.0 36.22 Wang et al. (2013a)
AC developed from tamarind wood 10e50 6.5 28.019 Acharya et al. (2009)
AC developed from date palm seed 20e125 1.0 120.48 Nemr et al. (2008)
PAC 50 3.0 43.29 this study

Fig. 4. Comparison of experimental and calculated effluent Cr(VI) concentration values: (a) Freundlich; (b) Langmuir.

above calculation method for the CTA process.
The validation of the calculation method and the improvement
in Cr(VI) removal are shown in Fig. 4. The abbreviations used in this
figure, including cal and exp stand for calculated and experimental,
respectively. The PAC dose of m=V ¼ 1.0 g/L in the Cr(VI) mixed
liquor could be converted to the PAC dose of raw Cr(VI) solution by
m=V  1:0V=0:8V ¼ 1.250 g/L. It is clear that Cr(VI) removal was
significantly improved by the CTA process compared with the CSA
process at the same PAC dose of 1.250 g/L. The calculated effluent
Cr(VI) concentrations were 20.22 mg/L (Freundlich) and 20.07 mg/L
(Langmuir) for the CSA process, which corresponded to Cr(VI)
removal efficiencies of 59.56% and 59.86% by isotherm equations at
the PAC dose of 1.250 g/L, respectively. For the CTA process, the
Cr(VI) concentration of the first effluent cycle was higher than that
of the subsequent effluent cycles due to the absence of loaded PAC
in the pressure cup at the initiation stage, which also affected the
Cr(VI) concentration during the second effluent cycle. The experi-
mental effluent Cr(VI) concentration data of the first and second
effluent cycles were excluded, and the average value of the other
seven effluent cycles was employed. The experimental average
effluent Cr(VI) concentration for the CTA process was 9.81 mg/L,
corresponding to a removal efficiency of 81.95%, that was approx-
imately 37% higher than that of the CSA for the same PAC dose of
1.250 g/L. The calculated average effluent Cr(VI) concentrations
were 10.65 mg/L (Freundlich) and 10.79 mg/L (Langmuir) for the
CTA process, corresponding to removal efficiencies of 78.70% and
78.42%, respectively. The experimental average Cr(VI) removal ef-
ficiency was slightly higher than the calculated averages because
the negligible third or even fourth stage adsorptions were not
considered in this study. However, this finding did not affect the
validity of the above calculation method. In terms of removal effi-
ciency, deviations of <5% between the experimental average
removal efficiency and the calculated averages demonstrated the
validity of the calculation method.
3.4.3. Comparison of PAC consumption
The advantage of the countercurrent adsorption process is the
PAC saving compared with sing-stage adsorption at the same
removal efficiency. Therefore, from another perspective, to achieve
the same effluent quality as the CTA process, i.e., an effluent Cr(VI)
concentration of 9.81 mg/L, the PAC dose required for the CSA
process could be calculated using Langmuir or Freundlich equation.
Table 3 shows that the PAC adsorption capacity was more effec-
tively exploited by the CTA process, so the PAC doses were 49.23%
(Langmuir) and 44.37% (Freundlich), which are lower than those of
the CSA process. For the same effluent quality, the PAC dose could
be reduced under the CTA process compared to that of the CSA.

Table 3
PAC dose and adsorption capacity for the CSA and CTA processes. 4. Conclusions
Parameters CSA CTA
The present study investigated the removal of Cr(VI) from
Langmuir Freundlich
aqueous solutions by adsorption over commercial PAC, and the
PAC dose (g/L) 2.462 2.247 1.250 adsorption of Cr(VI) was determined to be highly dependent on pH.
Relative PAC dose 1.970 1.798 1.000 The kinetic studies demonstrated that a pseudo-second-order
qe (mg/g) 16.32 17.89 32.15
model could provide a realistic description of Cr(VI) adsorption
102 W. Wang / Chemosphere 190 (2018) 97e102
kinetics. Both the Langmuir and Freundlich models fitted the
isotherm data well compared to the Temkin model. With CTA, the
Cr(VI) removal efficiency improved by approximately 37%
compared to the CSA at the same PAC dose of 1.250 g/L. The
calculation method for correlating the Cr(VI) removal efficiency and
the PAC dose base on the Langmuir and Freundlich models was
deduced and validated, and deviations of <5% between the exper-
imental average removal efficiency and the calculated averages
demonstrated that the calculation method was acceptable.
Acknowledgements
The authors are grateful for the financial support from the Talent
Introduction Subject of Dezhou University (No. 2015kjrc04).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2017.09.141.
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