Chemosphere 236 (2019) 124370

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

Removal of copper and cadmium ions from alkaline solutions using

chitosan-tannin functional paper materials as adsorbent
Haodong Sun, Nannan Xia 1, Zhongming Liu, Fangong Kong*, Shoujuan Wang**
State Key Laboratory of Biobased Material and Green Papermaking, Key Laboratory of Pulp & Paper Science and Technology of Shandong Province/Ministry
of Education, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, China

h i g h l i g h t s

An environment-friendly functional paper was used as an effective adsorption material.

The adsorption of Cu2þ and Cd2þ on functional paper followed a complexation-adsorption model.

This paper-based absorbent showed an excellent desorption capability and reusability.

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

Article history: We successfully absorbed the copper ion (Cu2þ) and cadmium ion (Cd2þ) from alkaline aqueous solutions
Received 13 June 2019 using the prepared chitosan-tannin (CTS/TA) functional paper as absorbent materials. The kinetics of the
Received in revised form adsorption, the adsorption isotherms, and the influence of the solution flow rate and pH were investi-
10 July 2019
gated detailly. The adsorption data were described well by Langmuir isotherms, with maximum copper
Accepted 13 July 2019
Available online 17 July 2019
(Cu2þ) and cadmium (Cd2þ) adsorption capacities of 684.93 and 813.01 mg/m2, respectively. The
experimental results also showed that the adsorption of these heavy metals was selective in the order of
Handling editor: Y Yeomin Yoon Cu2þ > Cd2þ, as Cu2þ competed with Cd2þ for bonding sites at solution concentrations greater than or
equal to 200 mg/L. The results of this study illustrated that the chitosan-tannin functional paper mate-
Keywords: rials mainly followed a complexation-adsorption model, and the best adsorption capacity was achieved
Chitosan-tannin functional paper at pH ¼ 9. The desorption of heavy ions from this adsorbent and its reusability of functional paper was
Copper also involved. Therefore, this novel, environment-friendly functional paper can surely act as an effective
Cadmium adsorbent for the removal and recovery of heavy metals in alkaline aqueous solutions.
Adsorption isotherm
© 2019 Elsevier Ltd. All rights reserved.
Adsorption kinetic
Desorption

1. Introduction
Industrially discharged wastewater likely contains various
heavy metals. As is well known, most of these metals are toxic and
carcinogenic agents and represent a severe threat to human health
as well as the animals and plants of the receiving water bodies
(Hokkanen et al., 2014; Piccolo et al., 2019; Xu et al., 2019; Zhou
et al., 2004). The global emissions of heavy metals, especially of
copper and cadmium, have become a significant problem. In
contrast to organic pollutants, the above-mentioned heavy metals
accumulate in a variety of animals and plants, as they cannot be
* Corresponding author.
** Corresponding author.
E-mail addresses: kfgwsj1566@163.com (F. Kong), wshj@qlu.edu.cn (S. Wang).
1
equal contributor as the first author.
biodegraded, and they are also carcinogenic or toxic when their
concentrations exceed certain tolerance levels (Kyzas et al., 2019;
Yuan et al., 2019). In addition, these substances tend to persist for
a long time in ecosystems and are difficult to eradicate. Sources of
these heavy metals are metal-plating and fabrication facilities,
illegal landfills, mining industry, fertilizers, and abandoned waste
disposal sites. Other sources of heavy metals include waste emis-
sions, atmospheric depositions, natural weathering processes, and
anthropogenic activities (Chen et al. 2008, 2009).
Copper and cadmium are common metal elements predomi-
nantly used in the production industry. Cu can spread through
natural phenomena and is widely used in the electrical industries
and antifouling paints (Arshad et al., 2019; Su et al., 2018; Wan
et al., 2010). Among the ionic species of copper, Cu ions are easily
attached to organic and inorganic substances depending on the pH
of the solution (Hasan et al., 2008; Sun et al., 2019; Zhao et al.,

https://doi.org/10.1016/j.chemosphere.2019.124370
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
2 H. Sun et al. / Chemosphere 236 (2019) 124370
2019). Furthermore, cadmium accumulates in the human body,
causing nausea, salivation, renal degradation, muscle cramps,
chronic pulmonary problems, and skeletal deformities. Human
health is threatened due to cadmium use from various sources, such
as photographic materials, pigments, printing, batteries, and ex-
plosives manufacturing (Boparai et al., 2011; Mohan et al., 2014;
Zhou et al., 2019).
Due to the negative effects of these contaminants, their removal
from wastewater has become an urgent concern. At present, some
solutions have been proposed and applied. The conventional
widely employed technologies for the removal of heavy metal ions
from wastewater are based on physicochemical processes, such as
ion exchange processes, separation through membranes, electro-
deposition techniques, adsorption, and chemical precipitation (Hao
et al., 2018; Liu et al., 2019; Ngah et al., 2005). However, these
methods have distinct limitations, are expensive, and may copro-
duce a large quantity of waste. Furthermore, they require peculiar
equipment and reagents. Considering the above disadvantages,
heavy metal ions should be removed via adsorption onto low-cost
materials (Bogusz et al., 2015). There are many adsorbent materials,
such as zeolites (Ji et al., 2012), clay (Ely et al., 2011), silica (Li et al.,
2011; McManamon et al., 2012), TiO2 (Vu et al., 2012; Zhang et al.,
2011), activated carbon (Jha et al., 2008; Ru et al., 2007), and syn-
thetic resins (Wang et al., 2011), which have been applied to handle
heavy metal ions.
Cellulose, the most abundant of all biopolymers, has been
studied over the past thirty years for its possible application in the
removal of heavy metals from wastewater (Kim et al., 2006;
Kumararaja et al., 2018; Stephen et al., 2011). However, it has a
limited number of adsorption sites, the stability is poor, and its
natural form is not ideal. In the past several years, magnetic hybrid
hydrogels have been prepared using a novel polymeric coating
consisting of chitosan (Kumararaja et al., 2018; Yi et al., 2015),
cellulose and functionalized cellulose nanofibers through electro-
spinning and modification with oxolane-2,5-dione (Stephen et al.,
Fig. 1. Schematic illustration of functional paper preparation and experimental procedure.
2011). These processes are more complicated and require signifi-
cant modifications of the cellulose.
Herein, a cellulosic paper with heavy metal adsorption capa-
bilities was prepared by employing functionalization strategies to
modify cellulose via the crosslinking of tannins with chitosan to
create functional paper materials using simple papermaking pro-
cesses, as shown in Fig. 1. The amino groups of chitosan can make
cellulosic fibers better bonded with tannic acid via electrostatic
interactions, and also the mechanical strength of paper can be
increased through adding chitosan. The tannic acid on/in this
functional paper could chelate with ions to remove the ions from
aqueous solution. The objectives of this work were to develop a
paper-based adsorbent with a low cost and high desorption per-
formance and to investigate its application with simulated heavy-
metal-laden wastewater, and to understand the adsorption ki-
netics of heavy ions on this functional paper-based adsorbent.
2. Materials and methods
2.1. Chemicals and reagents
Cellulose was obtained from the Shandong Sun Paper Group in
the form of pulp board (Yanzhou, Shandong, China). Tannin, chi-
tosan, methyl alcohol (99.5%, v/v), chloroform, acetic acid, sodium
citrate (375 g/L), hydroxylamine hydrochloride (100 g/L), ammo-
nium hydroxide (5 mol/L), and 2,9-dimethyl-1,10-phenanthroline
were obtained from Sigma-Aldrich Co., Ltd., (Shanghai, China)
and were used as received without further purification. Solutions of
Cu2þ and Cd2þ ions were prepared by dissolving certain quantities
of copper and cadmium particles in nitric acid (5.07 mol/L)
(Shanghai Aladdin Reagent Co., Ltd., Shanghai China). Furthermore,
hydrochloric acid (1 mol/L) and ammonium hydroxide (1 mol/L)
solutions were used for the pH adjustment of the solutions. Ultra-
pure water was used for the dilutions and reagent preparation, and
all chemical reagents were of analytical grade.
 H. Sun et al. / Chemosphere 236 (2019) 124370
2.2. Preparation of the chitosan-tannin functional paper
Coniferous wood pulp board (500 g, moisture content 8.0%) was
torn into pieces with diameter of 4e5 cm, and then the pulp pieces
were put into Valley beater KRK2505 (Japan) followed with addi-
tion of 23 L water. The pulp was beaten in Valley beater to 35 ± 2
o
SR beating degree. After that, the pulp was dehydrated for 2 min in
dehydrator. Modified cellulosic pulp was prepared by stirring 17 g
of pulp in 1600 mL of aqueous solution in a fiber dissociator (4000
r/min), 30 mL of 10% tannin acid, and 100 mL of 0.1% chitosan in
30:1 (g/g) using magnetic stirring at room temperature for 16 h.
Paper-sheet forming was performed on a paper sheet former by
pouring the pulp slurry into the bowl of the paper-sheet former,
followed by draining the slurry through a metallic wire. The wet
paper sheet was dried at 50  C to get the desired chitosan-tannin-
modified paper. The tannic acid content of prepared chitosan-
tannin-modified paper is 32.36 g/m2.
2.3. Characterization of the chitosan-tannin functional paper
The morphology of the chitosan-tannin functional paper was
observed using a COXEMEM-30 PLUS SEM (Daejeon, Korea). Fourier
transform infrared spectroscopy (FTIR) spectra were recorded using
a Bruker VERTEX70 FTIR (Karlsruhe, Germany) spectrophotometer
between 400 and 4000 cm1 with a resolution of 4 cm1 using the
attenuated total reflectance (ATR) spectra.
2.4. Adsorption
All the adsorption experiments were carried out using contin-
uous sample introduction systems. First, the paper sheet was cut
into two round pieces ~5 cm in diameter, which were spread in a
glass funnel. Second, the heavy metal ion solution was diluted in
10 mL of ultrapure water at a desired concentration. Ultimately, the
heavy metal solution was slowly trickled into the glass funnel
containing the paper sheet, and the flow rate was controlled by
adjusting the peristaltic pump. After adsorption, the concentration
of copper ions was obtained using a UVeVis spectrophotometer
(UV-VIS-NIR Agilent Cary5000) at 457 nm with 2,9-dimethyl-1,10-
phenanthroline as a colorimetric reagent based on a previously
described method (Yi et al., 2015), and the concentration of cad-
mium ions was analyzed using a flame atomic absorption spec-
trometer (AAS, GGX-600, China). For the measurement of cadmium
ion equilibrium concentration, a hollow cathode lamp was used.
The amount of adsorbed metal ions was calculated using the
equations shown below.
The number of copper ions adsorbed onto the paper was
calculated by the formula:
ðC 0  CÞV
M¼  M0; (1)
1000S
where M is the copper ion adsorption capacity of the modified
paper, mg/m2; M0 is the copper ion adsorption capacity of the
original paper, mg/m2; C0 and C are the copper ion concentrations
in the solutions before and after adsorption, respectively, mg/L; V is
the volume of the solution, mL; and S is the area of the paper, m2.
The cadmium adsorption amount at equilibrium was calculated
using the following equation:
ðC i  C t ÞV 0
A¼ ; (2)
1000G
where A is the cadmium ion adsorption capacity of the modified
paper, mg/m2; Ci is the initial cadmium ion concentration in the
3
solution, mg/L; Ct is the equilibrium concentration of heavy metal
ions in the solution, mg/L; V is the volume of the initial solutions,
mL; and G is the area of the paper, m2.
2.5. The effect of solution pH
The effect of the solution pH on the adsorption of Cu2þ and Cd2þ
ions on the tested functional paper was studied. In this step, the
initial pH value of the solution was adjusted to be in the 2e10 range
for Cu2þ and Cd2þ while maintaining the heavy metal ion con-
centration 100 mg/L, and the solution flow rate was 60 mL/h. The
main objective was to determine the best pH for combining tannic
acid with boric acid.
2.6. Optimum of a solution flow rate
The impact of the solution flow rate, which was varied in the
range of 40e120 mL/h, on the adsorption of the heavy metal ions
was examined using a series of solutions while maintaining the
same concentrations of copper and cadmium (200 mg/L), area of
the functional paper (3.18  103 m2), and pH value (9). The flow
rate of the solution was controlled using a peristaltic pump. The
flow rate of keeping other factors unchanged, the velocity of the
solution was varied to explore the effect on the adsorption of heavy
metals by the functional paper.
2.7. Kinetic study
The adsorption kinetics were investigated to explain the
adsorption mechanism and characteristics.
First, the effect of time on the adsorption of heavy metal ions
onto the functional paper was investigated over a total reaction
time of 24 h for the Cu2þ and Cd2þ ions. The amount of adsorbent
was 0.5 g, the area was 3.18  103 m2, and the initial concentra-
tions of the individual heavy metal ions in the single element so-
lutions were 100, 200, and 300 mg/L. The pH values were adjusted
to 9 for the Cu2þ and Cd2þ ion solutions. The heavy metals were
adsorbed by filtration, and the filtrates were used to analyze the
heavy metal concentrations.
2.8. Adsorption isotherms
The adsorption capacities for Cu2þ and Cd2þ ions of the
chitosan-tannin functional paper were obtained based on the initial
adsorption isotherms of each ion. The adsorption isotherms were
obtained at an initial pH of 9 for the Cu2þ and Cd2þ ions. The heavy
metal concentrations were in the 50e500 mg/L range. The single
adsorption systems contained 10 mL of solution and total areas of
3.18  103 m2 of the functional paper. The solutions were filtered
through a bush funnel with the functional paper.
2.9. Desorption and regeneration
First, 50 mL of Cu2þ and Cd2þ ion solutions (with an initial
concentration of 200 mg/L, solution pH value of 9) was added to a
bush funnel with the functional paper. The solution flow rate was
varied within the 15e240 mL/h range, and the flow rate of the so-
lution was controlled by a peristaltic pump. After desorption, the
paper was recycled and made into pulp to study the regeneration
process. Desorption rate of the heavy metals was calculated as
follows:
4 H. Sun et al. / Chemosphere 236 (2019) 124370

CT V T
E% ¼  100%; (3)
A

where CT denotes the detected concentration of heavy metals in the

desorption solution, mg/L; VT is the volume of the desorption so-
lutions, mL; and A is the adsorption capacity of the modified paper
to boric acid, mg/m2.

2.10. Data analysis

To investigate the mechanism of the adsorption kinetics, we

used the following two equations. The kinetics data were obtained
using the pseudo-first-order rate equation of Lagergren and Kun-
gliga, expressed as follows:

lnðqe  qt Þ ¼ lnqe  K 1 t; (4)

and the pseudo-second-order rate equation of Ho and McKay,

expressed as follows:
Fig. 2. (a) SEM images of original paper and (b) chitosan-tannin functional paper.
t 1 1
¼ þ t; (5)
qt K 2 q2e qe
corresponding to the stretching vibrations of eC]O, eC]Ce of the
where qe is the amount of heavy metal adsorbed at saturation, mg/ benzene ring, and eCeOe in the tannin, respectively. Thus, chito-
m2; qt is the amount of heavy metal adsorbed at any time t, mg/m2; san could significantly promote flocculation of the tannin in the
t is the contact time, h; and K1 (1/h) and K2 (m2/mg h) are the rate chitosan-tannin-modified paper.
constants of the pseudo-first-order and pseudo-second-order
equation, respectively. 3.2. Effect of the pH value on adsorption
The Langmuir equation, which is valid for monolayer adsorption
onto a surface with a finite number of identical sites, can be The pH of an aqueous solution is an important parameter for the
expressed as follows:
adsorption of metal ions from solution onto an adsorbent (Zheng
et al., 2012). As shown in Fig. 4a, the adsorption of Cu2þ and Cd2þ
Ce Ce 1
¼ þ ; (6) ions onto the chitosan-tannin functional paper was strongly
qe Q m bQ m
dependent on the pH of the solution. The adsorption capacity
increased with increasing pH until it plateaued at pH 9. The
where Ce is the equilibrium copper concentration, mg/L; qe is the
adsorption capacities of the modified paper for copper and cad-
amount of copper adsorbed at equilibrium, mg/m2; Qm is the
mium ions in alkaline or neutral solutions were better than those in
maximum adsorption capacity of adsorbent, mg/m2; and b is the
the strongly acidic solution. At lower pH values, hydrogen ions
“affinity parameter” or Langmuir constant, L/mg.
strongly competed with metal ions for the same negatively charged
The linear form of the Freundlich equation, another widely used
adsorption sites on the surface of the adsorbent. As the solution pH
empirical equation derived to model the multilayer adsorption, can
value increased, the concentration of competitive hydrogen ions
be represented as follows:
decreased, and this increased the heavy metal adsorption capacity.
1 In this study, the optimum pH value for the adsorption of Cu2þ and
lnqe ¼ lnK F þ lnC e ; (7) Cd2þ ions was determined to be 9, as this allowed the heavy metal
n
ions to easily adsorb via the catechol ligand complexes. In addition,
where qe and Ce are defined above, KF is the Freundlich constant (L/ at a pH of 10, the adsorption efficiency decreased due to the
mg), and n is the heterogeneity factor. possible oxidation of catechol {{}}groups.

3. Result and discussion 3.3. Effect of the flow rate on adsorption

3.1. Characterization of chitosan-tannin functional paper
The morphological characteristics of the original and chitosan-
tannin-modified paper were investigated by scanning electron
microscopy (SEM) [see Fig. 2 (a) and (b)]. The cellulose fiber density
of the chitosan-tannin-modified paper was higher than that of the
base paper. The chitosan produced flocculation effects on the paper,
and the tannin and chitosan played important roles in crosslinking
of the paper. Furthermore, the structures of the original and
chitosan-tannin-modified paper were analyzed using FT-IR, and the
obtained spectra are presented in Fig. 3. The spectra of three
different regions were examined, including several bands in the
10002000 cm1 range. The chitosan-tannin-modified paper
showed three obvious peaks at 1688, 1600, and 1200 cm1,
The adsorption data at different flow rates of copper and cad-
mium solutions with different papers are shown in Fig. 4b. The CTS/
TA paper plots showed that the adsorption of copper and cadmium
consisted of two phases; an initial rapid phase where the adsorp-
tion capacity was high, and a second slower phase where the
adsorption capacity was low. The maximum amounts of copper and
cadmium adsorbed were 373 and 439.87 mg/m2 for the solution
flow rate of 40 mL/h. However, the maximum copper and cadmium
adsorption capacities were, respectively, 126.8 and 83 mg/m2 for
the TA paper and 113.3 and 82 mg/m2 for the CTS paper. The
adsorption data indicated that chitosan is a great initiator to in-
crease the flocculation of tannic acid. The increase in the adsorption
capacity with decreasing heavy metal solution flow rate could be
due to a higher probability of collision between the heavy metal
 H. Sun et al. / Chemosphere 236 (2019) 124370 5

Fig. 3. FT-IR spectra of the original and modified paper.

Fig. 4. (a) Effect of solution pH on copper and cadmium ion adsorption capacity at 100 mg/L and 60 mL/h. (b) Effect of velocity on the adsorption of copper and cadmium ions by
different papers at 200 mg/L and pH ¼ 9.

ions and adsorbent surface.
3.4. Kinetics of adsorption
The adsorption of copper and cadmium on the chitosan-tannin
functional paper was examined as a function of contact time for
various initial adsorption concentrations. As shown in Fig. 5, the
adsorption of copper and cadmium achieved an equilibrium state
after 17 h. The adsorption reaction occurred rapidly within the first
hour, which was likely due to high availability of active sites on the
adsorbent. The active sites had a tendency to saturate with
increased contact time, and the reaction system finally reached
sorption equilibrium after 24 h. As shown in Fig. 5a and b, qt of the
CTS/TA paper for Cu2þ and Cd2þ increased with an increase in the
initial heavy metal ion concentration. This may have been due to
the high driving force for mass transfer at high ion concentrations
(Taty-Costodes et al., 2003; Zhang et al., 2018). Adsorption data
were obtained from Eqs. (4) and (5), and the results are shown in
Figs. 6 and 7. The value of the correlation coefficients and rate
constants are given in Table 1. As shown in Figs. 6 and 7, the
adsorption kinetics of Cu2þ and Cd2þ on the CTS/TA paper followed
the pseudo-second-order model. Meanwhile, as shown in Table 1,
the correlation coefficients were the highest (R2 > 0.9999) for the
pseudo-second-order model, and the calculated qe value agreed

Fig. 5. Effect of the contact time on (a) copper and (b) cadmium ion adsorption capacities by the CTS/TA paper. Reaction conditions: initial metal ion concentration ¼ 200 mg/L;
solution pH ¼ 9.
6 H. Sun et al. / Chemosphere 236 (2019) 124370

Fig. 6. Pseudo-first-order plot for the adsorption of (a) copper and (b) cadmium ions on the CTS/TA paper.

Fig. 7. Pseudo-second-order plot for the adsorption of (a) copper and (b) cadmium ions on the CTS/TA paper.

Table 1
Kinetic parameters for the adsorption of Cu2þ and Cd2þ on CTS/TA paper.

Metal ions Concentration (mg/L) Pseudo-first-order model qe (exp) (mg/m2) Pseudo-second-order model
1 2 2
K1 (h ) qe (mg/m ) R K2 (m2/mg. h) qe (mg/m2) R2
2þ
Cu 100 1.8322 40.25 0.9638 308.384 0.0467 309.60 0.9999
200 1.7576 61.51 0.9453 539.792 0.0319 540.54 0.9999
300 1.5758 97.46 0.9686 639.361 0.0256 641.03 0.9999
Cd2þ 100 2.0623 99.32 0.9823 289.196 0.0234 290.70 0.9999
200 1.7366 129.91 0.9358 596.876 0.0170 598.80 0.9999
300 1.1751 174.87 0.9762 805.103 0.0173 806.45 0.9999

with the experimental data from the second-order equation, which
suggests that it was suitable for the entire adsorption process. Thus,
chemisorption was the rate-limiting mechanism for the adsorption
of Cu2þ and Cd2þ onto the CTS/TA paper.
3.5. Effect of metal ion concentration and adsorption isotherm
The Cu2þ and Cd2þ ions adsorption isotherms were investigated
at different initial concentrations ranging from 50 to 500 mg/L and
are shown in Fig. 8a and b. The amount of adsorbed Cu2þ and Cd2þ
 H. Sun et al. / Chemosphere 236 (2019) 124370 7

Fig. 8. Effect of the concentration on (a) Cu2þ and (b) Cd2þ adsorption at 200 mg/L and pH ¼ 9. (c) Langmuir isotherm plot and (d) Freundlich isotherm plot for adsorption of metal
ions on the chitosan-tannin-modified paper surface.

increased with the increase in the equilibrium concentration. Cor- Table 3

relation coefficients and adsorption constants for Cu2þ and Cd2þ Adsorption of copper and cadmium from single and binary metal solutions by the
CTS/TA paper.
onto the CTS/TA paper acquired using Langmuir and Freundlich
isotherms are given in Table 2. The correlation coefficients Heavy metal concentration Heavy metal adsorption capacity (mg/
confirmed that the Langmuir model fit the data better than the m2)

Freundlich model (R2 > 0.9846 for the Langmuir model vs Cu Cd Cu þ Cd

0.981e0.984 for the Freundlich model). The values of n (>1) indi- 50 mg/L Cu or Cd 107 106.0 e
cated favorable conditions and good adsorption onto the TA/CTS 50 mg/L Cu þ 50 mg/L Cd 106 98.3 204.3
paper. 100 mg/L Cu or Cd 195 201.0 e
100 mg/L Cu þ 100 mg/L Cd 194 205.7 399.7
The Langmuir isotherm model is most suitable for monolayer
150 mg/L Cu or Cd 284 287.0 e
adsorption based on the assumption that there are finite numbers 150 mg/L Cu þ 150 mg/L Cd 249 257.7 506.7
of identical sites. The maximum adsorption capacities of the CTS/TA 200 mg/L Cu or Cd 363 363.0 e
paper for Cu2þ and Cd2þ ions were 684.93 and 813.01 mg/m2, 200 mg/L Cu þ 200 mg/L Cd 349 297.1 646.1
respectively. Obviously, the Cu2þ and Cd2þ ions adsorption perfor- 300 mg/L Cu or Cd 471 500.0 e
300 mg/L Cu þ 300 mg/L Cd 450 236.2 686.2
mance of TA/CTS paper were superior to those of previously re-
ported absorbents in alkaline conditions, including traditional
graphene oxide (Sherlala et al., 2018), activated carbon (Orbecido
et al., 2019), biochar (Goh et al., 2019) and sugarcane bagasse TA paper or that there are excess binding sites and infrequent
(Xavier et al., 2018). Moreover, the TA/CTS paper was environment competition of adsorption active sites. However, these results
friendly, more facile, cost-effective and easier to scale up. This changed dramatically with high solution concentrations (greater
suggests the effectiveness of the TA/CTS paper as a potential than or equal to 200 mg/L Cu2þ or Cd2þ). The Cd2þ adsorption ca-
adsorbent for the treatment of water containing copper and pacity of the CTS/TA paper decreased by approximately 18e52.8%
cadmium. with increased heavy metal concentration. These results clearly
indicate that Cu2þ can compete with Cd2þ for binding sites at
higher heavy metal concentrations. This competitive relationship is
3.6. Adsorption of Cu2þ and Cd2þ in a binary-solution system possibly due to the higher affinity of the CTS/TA paper for Cu2þ than
for Cd2þ, and thus, the copper can preferentially react with func-
Under natural circumstances, heavy metals are rarely present tional paper adsorption sites over cadmium. This comparison
alone, and they interact with each other and other matrix compo- suggests that we should consider the effect of different solution
nents, which is known to influence their fate and transport in the concentrations on the heavy metal effluent treatment.
environment (Chen et al., 2011). Since urban industrial wastewater
often contains Cu2þ and Cd2þ, their competitive adsorption char-
acteristics in single and binary metal solutions were investigated, 3.7. Desorption and regeneration studies
and the results are shown in Table 3. The adsorption data un-
equivocally indicate that the adsorption of copper or cadmium onto From a practical point of view, repeated recycling is important
CTS/TA paper was only slightly influenced by the presence of the for adsorbents (Bogusz et al., 2015). If the adsorbent has a higher
other metals in solution at low initial concentrations (less than or adsorption capacity and better desorption performance, this will
equal to 150 mg/L Cu2þ or Cd2þ). Thus, at low concentrations, heavy reduce the total cost of the adsorbent. To investigate the possibility
metal ions either bind to different active sites on the surface of CTS/ of reusability of the TA/CTS paper as an adsorbent, we performed

Table 2
Adsorption isotherm parameters for Cu2þ and Cd2þ adsorption on the CTS/TA paper.

Metal ions Langmuir isotherm constants Freundlich isotherm constants

b (L/m2) Qm (mg/m2) R2 KF (mg/m2)(L/m2) N R2

2þ
Cu 0.0125 684.93 0.9904 20.008 1.5793 0.981
Cd2þ 0.0098 813.01 0.9846 17.709 1.4909 0.984
8 H. Sun et al. / Chemosphere 236 (2019) 124370
Fig. 9. (a) Effect of the flow rate on desorption of Cu2þ and Cd2þ from the CTS/TA paper in 0.1 M citric acid solution. (b) Performance of CTS/TA by secondary cycles of regeneration.
Reaction conditions: initial metal ions concentration ¼ 200 mg/L; solution pH ¼ 9; flow rate of solution ¼ 60 mL/h.
desorption and secondary recovery experiments, the results of
which are shown in Fig. 9. Desorption of Cu2þ and Cd2þ from the
TA/CTS paper was achieved using 0.1 M citric acid. The reusability
was demonstrated by following the adsorption-desorption for
different flow rates of Cu2þ and Cd2þ solutions. The desorption
efficiency of Cu2þ and Cd2þ is shown in Fig. 9a. As the flow rate
increased, the desorption capacity of the copper ions remained
above 96.14%, and that of the cadmium ions remained above 92%.
With a five-time flow rate increase, the desorption rate remained
almost unchanged. As shown in Fig. 9b, the heavy metal adsorption
capacity of CTS/TA paper slightly decline for the secondary circu-
lation, indicating that there were few irreversible sites on the sur-
face of the CTS/TA paper. Our reusability research suggested that
the TA/CTS paper can be used as an efficient adsorbent in heavy
metal wastewater treatment.
4. Conclusions
In this study, a new functional paper for heavy metal ion
adsorption was prepared through the simple cross-linking of
cellulosic fibers and tannin with chitosan. Heavy metal concen-
trations effectively decreased due to metal complex formation be-
tween the catechol of the tannin and heavy metal ions with less
activity loss under alkaline conditions. Moreover, this material
exhibited good and stable desorption abilities for heavy metals in
acidic solutions due to dissociation of the metal complexes be-
tween the tannin and heavy metals. Although Cu2þ adsorption was
only marginally affected by Cd2þ, Cu2þ competed with Cd2þ for
binding sites at Cu2þ and Cd2þ concentrations greater than or equal
to 200 mg/L. The results indicated that CTS/TA paper's cheap
feedstock, simple methods of preparation, regeneration, fast
adsorption of heavy metal ions from alkaline solutions, and great
adsorption capacity make the CTS/TA paper a useful and econom-
ically viable adsorbent for the removal of heavy metals from
wastewater.
Acknowledgments
The authors are grateful for the National Natural Science
Foundation of China (Grant No.31570566. 31600472), the Natural
Science Foundation of Shandong (ZR2017LEM009,
ZR2018BEM026), the Key Research and Development Program of
Shandong Province (No. 2017GSF17130), National Key R&D Pro-
gram of China（No. 2017YFB0308000). We thank LetPub (www.
letpub.com) for its linguistic assistance during the preparation of
this manuscript.
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