Industrial Crops and Products 34 (2011) 12381240

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Industrial Crops and Products

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Short communication

Caesalpinia spinosa and Castanea sativa tannins: A new source of biopolymers

with adsorbent capacity. Preliminary assessment on cationic dye removal
J. Snchez-Martn , J. Beltrn-Heredia, J. Gragera-Carvajal
Universidad de Extremadura, Department of Chemical Engineering and Physical Chemistry, Avda. de Elvas, s/n, 06071 Badajoz, Spain

a r t i c l e

i n f o

Article history:
Received 24 January 2011
Received in revised form 11 March 2011
Accepted 20 March 2011
Available online 13 May 2011
Keywords:
Caesalpinia spinosa
Castanea sativa
Tannin
Dye removal
Natural adsorbents
Gelication

a b s t r a c t
Tannins from Caesalpinia spinosa (Tara) and Castanea sativa (Chestnut) have been tested for gelication.
Adsorbent are produced by formaldehyde-induced polymerization (TTG for Tara, CTG for Chestnut). These
new biopolymers were tested for cationic dye removal and promising results were achieved: gelied
tannins from both natural vegetal sources were effective in removing Victoria Blue R, Methylene Blue
(MB) and Fuchsine, while Auramine O and Rhodamine B were refractory to this treatment. The particular
case of CTG-MB is ruled by Langmuir adsorption hypothesis. kl1 and kl2 parameters are obtained for
four different temperatures according to linear, non linear and multiparametric adjustment. Good r2
correlation coefcients are obtained in every case.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The increasing pollution level urges scientic community to
research with more and more dedication in environmental remediation. In addition, natural resources are becoming relevant in this
task because they present many advantages that t very well to the
sustainability soope (Dorf, 2001). Proting the numerous chemical
compounds that come from vegetal world may be an interesting
way for the synthesis of useful products. In this scenario, tannins
have been already used as natural adsorbents, after undergoing a
gelication process (Nakano et al., 2001; Tondi et al., 2009; BeltrnHeredia et al., 2011).
The remediation of several pollution problems is a target of
many researchers nowadays. Technical ways of solving environmental concerns and menaces such as the dumping of surfactants,
dyes, pharmaceuticals and other hazards are available long time
ago, but making them cheaper and sustainable is still a challenge.
Natural raw materials are a possible source of low-cost adsorbents
that could provide a successful solution (Demirbas, 2008; Mohan
et al., 2008).
Tannin structure involves multiple aromatic rings that provides a useful matrix in which active centers can be introduced
by means of the adequate polymerization process (Pizzi, 2008).

Corresponding author. Tel.: +34 924289 300x9033; fax: +34 924289 385.
E-mail addresses: jsanmar@unex.es (J. Snchez-Martn), jbelther@unex.es
(J. Beltrn-Heredia), jugragera@alumnos.unex.es (J. Gragera-Carvajal).
0926-6690/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2011.03.024

Two classes of chemical compounds of mainly phenolic nature are

included as vegetable tannins: condensed and hydrolysable tannins
(Hagerman, 1995).
Hydrolysable tannins, including Castanea sativa or Caesalpinia
spinosa in a percentage, are reputed to be mixtures of simple
phenols such as gallic and ellagic acids. They can form complex structures through formaldehyde polymerization although the
yield is much lower than in case of condensed tannins (Pizzi, 1994).
Regarding these two main structures, although hydrolysable tannins can be considered a quite entire group, signicative differences
may be observed depending on the predominant gallic or ellagic
building blocs (Pizzi, 2003).
Tannins from C. sativa (ellagitannin) present positional isomers castalagin and vescalagin, and previous investigations have
reported an important percentage of other molecules such as
castalin, acutissimin A, kurigalin or chestanin (Lampire et al., 1998).
Evidences of ellagitannin dimerization and hydrolysis are reported
(zacar and Sengil, 2003), so structural block grows therefore.
On the other hand, C. spinosa (Tara) presents a gallotannin
majority (Haslam, 1989). Tara is a tropical tree that was considered
the second tannin feed stock (behind Schinopsis balansae (Quebracho)) until Acacia mearnsii was harvested for this purpose. Gallic
acid included in the tannin structure of Tara has been considered
previously as a possible material for formaldehyde polymerization,
regarding its previsible higher yield than other hydrolysable tannins (Glvez-Garro et al., 1997).
The main aim of this contribution is to investigate these novel
adsorbents (Tara Tanning Gel (TTG) and Chestnut Tannin Gel (CTG))

J. Snchez-Martn et al. / Industrial Crops and Products 34 (2011) 12381240

1239

in the eld of cationic dyes removal. A preliminary screening for dye

removal potential of these two tannin-based adsorbent was carried out. The differences between tannin gel from these two tannin
sources have been pointed out by studying the interaction between
them and Methylene Blue (MB). Furthermore, equilibrium studies
of CTG-MB adsorption system have been carried out.
2. Materials and methods
2.1. Tannin extracts
TTG and CTG were prepared according to Nakano et al. (2001).
C. spinosa was kindly supplied by RAOUL-DUVAL Inc. (France). C.
sativa was provided by TANAC Inc. (Brazil). The exact preparation procedure of the tanningel is thorougly described elsewhere
(Beltrn-Heredia et al., 2011). Dyes were Auramine O (Basic Yellow 5, ALDRICH), Fuchsine (Basic Violet 14, ALDRICH), Victoria Blue
R (Basic Blue 11, ALDRICH), Rhodamine B (Basic Violet 10, ALFAAESAR) and Methylene Blue (Basic Blue 9, PANREAC).
2.2. General dye removal assay
Dye stock solution with a concentration equal to 1000 mg L1
was prepared. Different volumes of this initial solution were put
into 100 mL-ask in order to obtain the adequate initial dye concentration (IDC), and a xed quantity of adsorbent was added (20 mg)
in a pH 7 buffered media. Magnetic stirring was applied for 15
days in a magnetic multistirrer (SELECTA), until equilibrium was
achieved. Kinetics were carried out for conrming this aspect. The
slow kinetics this adsorbents seem to present has to do with the
non porous surface. The chemisorption must be governed by the
external diffusion stage, so that the adsorption process must take
place on the surface at regularly distributed active centers (BeltrnHeredia et al., 2011). Then, a sample was taken and centrifuged.
Photometric analysis was carried out in a 1-cm glass cell at corresponding maximum wavelength (different for each colorant).
An HELIOS UV/VIS spectrophotometer was used for photometric
measures.
Non-linear and multiparametric data adjustment were carried
out by using SPSS 15.0.1 for Windows.
3. Results and discussion
3.1. Preliminary screening for dye removal
As a rst step in the research process, the ability of the two
tannin gel products was tested with different cationic dyes. Trials
were performed with a xed initial dye concentration and with
xed mass of tannin gel. Fig. 1 reports the percentual removal for
each type of dye.
Similar rates of dye removal are obtained in both cases (CTG and
TTG) so the adsorption process is quite analogous with each product. Chemical structures of dyes can support the fact that the afnity
between tannin gel and Auramine O and Rhodamine B seems to be
lower due to the lack of positive charges (Auramine O) and the large
Rhodamine B molecule that surely difcults the adsorption due to
steric reasons. The rest of dyes presents either positive charges
(Methylene Blue or Victoria Blue) or a very well-balanced small
molecular weight (Fuchsine). This last case is removed by CTG in a
signicantly higher percentage.
4. Theoretical adsorption equilibrium modeling
In order to characterize the adsorption phenomenon, Langmuirs theoretical model is proposed since it is the main model
considered in this kind of adsorption process (involving monolayer

Fig. 1. Preliminary screening for dye removal.

and surface aggregation). It is well known that Langmuir hypothesis

follows Eq. (1):
q = kl1

Cl
1 + kl2 Cl

(1)

where kl1 is the rst Langmuir adsorption constant (L[g of

adsorbent]1 ) and kl2 is the second Langmuir adsorption constant
(L [mg of dye]1 ).
A non-linear data adjustment is made on the basis of kl1 and
kl2 are temperature-dependent, so different values are obtained at
each series. Table 1 refers the statistical summary of this adjustment. As can be appreciated, the adjusted correlation factor r2 is
quite high in every case (always above 0.75). This is the mathematical expression of the accuracy of the model, since more than 75%
of the experimental process can be interpreted by this model.
Fitting experimental data with the linear form of Langmuir
model (Eq. (2)) can be used for conrming the goodness of the
adsorption hypothesis in the current case:
k
Cl
1
+ l2 Cl
=
q
kl1
kl1

(2)

For each temperature, Eq. (2) has been applied to experimental

data. Linear correlations have been achieved as presented in Table 1.
As it is showed, in the studied interval of 283313 K four linear
Table 1
Adjustment parameters in Langmuir hypothesis. Units in text.
kl1
Non-linear adjustment
108.01
10 C
20 C
70.43
83.74
30 C
61.64
40 C
Linear adjustment

105.48
10 C
20 C
56.17
78.74
30 C
52.63
40 C

kl2

r2

0.284
0.119
0.127
0.062

0.786
0.808
0.923
0.808

0.27
0.091
0.11
0.05

0.994
0.958
0.991
0.851

Multiparametric adjustment
E1 = 6.36 103 ; E2 = 5.35 103 ; k01 = 1.016 103 ; k02 = 4.98; r2 = 0.801

1240

J. Snchez-Martn et al. / Industrial Crops and Products 34 (2011) 12381240

the temperature. Other natural materials such as activated carbon

from coconut husk (435 mgg1 in Tan et al. (2008)) or bamboo
(143 mgg1 in Kannan and Sundaram (2001)) presented lower
capacity. These tannin derived materials are consequently of great
interest.
5. Conclusions
This investigation has been focused on characterizing the ability
of new adsorbents based on Chestnut and Tara tannins. The gelication of these vegetal products is made with a well-known agent
(formaldehyde) so the instrumentation difcult is quite low. The
results are promising in removing at least three of the ve cationic
dyes that have been tested in this study. The adsorption process, in
the case of MB and CTG, follows a Langmuir classic model.
Acknowledgments

Fig. 2. Langmuir non-linear and multiparametric modelization of CTG-MB system.

expressions are found, so Langmuir model ts with an average r2

of 0.94.
The nonlinear Langmuir ts for the specic temperatures gave
lower correlation coefcients (mean of 0.83) because the error bars
are wider. However, previous studies have shown this method to be
more accurate than linear ts (Kumar and Sivanesan, 2006; Kumar
et al., 2008).
4.1. Multiparametric adjustment
By generalizing Langmuir hypothesis, temperature can be
included in the modelization by considering Langmuir constants
according to Arrhenius expressions. That assumes that kl1 and kl2
may have the following form:

k = k0 exp

E
RT

(3)

and taking logarithms and re-arranging:

ln k =

 E 1

+ ln k0

(4)

where k0 is the basic constant, whose units are equal to k, E is

the activation energy (Jmol1 ), R is the universal constant for perfect gases (J(molK)1 ) and T is the temperature of the adsorption
process (K).
The inclusion of denition (3) into Langmuir expression (Eq. (1))
leads to the expression (5):
q=

k01 exp ((E1 /R T )) Cl

1 + k02 exp ((E2 /R T )) Cl

(5)

Fig. 2 shows the experimental q data and the predicted ones by

these three adjustment procedures: linear, non-linear and multiparametric. Both non-linear and multiparametric procedures gives
a more accurate idea of the goodness of the model, while linear
regression checks the adequacy of Langmuirs hypothesis in this
adsorption process. In addition, multiparametric adjustment gives
us two more data: activation energies. According to the mathematical results, the values of these parameters (which gives us an idea
of the adsorption and desorption processes) are comparable. Minus
sign behind the activation energy E2 means the desorption process
is not favoured. It was observed and predicted some years ago by
Mozurkewich and Benson (1984), Mozurkewich et al. (1984) and
more recently by Nagao et al. (2008).
These adsorbents are competitive with other ones that are currently in use. Maximum adsorbent capacity in the case ot the
system CTG-MB falls between 300 and 750 mgg1 depending on

This investigation has been supported by COMISIN INTERMINISTERIAL DE CIENCIA Y TECNOLOGA (CICYT) CTQ 2010-14823/PPQ
project as well as to JUNTA DE EXTREMADURA under PRI-07A031
project.
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