Food Control 47 (2015) 536e544

Contents lists available at ScienceDirect

Food Control
journal homepage: www.elsevier.com/locate/foodcont

Natural clay and commercial activated charcoal: Properties and

application for the removal of copper from cachaça
Lidiany Mendonça Zacaroni a, Zuy Maria Magriotis a, Maria das Graças Cardoso a, *,
~o Guilherme Mendonça a, Sara S. Vieira a,
Wilder Douglas Santiago a, Joa
b
David Lee Nelson
a
Department of Chemistry, Federal University of Lavras, C.P. 3037, 37200-000 Lavras, Minas Gerais, Brazil
b
Pro-Reitoria de Pesquisa e Po ~o, Federal University of the Jequitinhonha and Mucuri Valleys, 39100-000 Diamantina, MG, Brazil
s-Graduaça

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

Article history: The influence of contact time and the amount of adsorbent on the removal of copper from distilled
Received 4 December 2013 cachaça was evaluated. The adsorption of copper was favored by a 1:50 ratio of mass of adsorbent (g) to
Received in revised form volume of sugar cane spirits (mL). An equilibration time of 120 min for clay and 360 min for activated
26 June 2014
charcoal resulted in the removal of 68.7% and 98.3% of the copper, respectivamente. The isotherms were
Accepted 20 July 2014
studied in the range of copper concentrations of 0 to 2000 mg L
1. The amount of copper adsorbed per
Available online 28 July 2014
unit weight of clay was 10.8 mg g
1, and for charcoal, it was 5.9 mg g
1. The isotherm results were tested
in the Langmuir and Freundlich models and were found to adapt better to the Freundlich model. The
Keywords:
Sugar cane spirits
removal of copper by clay and activated charcoal could be explained by a pseudo-second-order kinetic
Copper model. Given the organic and inorganic complexity of cachaça, the influence of this process on the flavor
Adsorption of the beverage was also evaluated. To this end, the analyses of aldehydes, higher alcohols, furfural, esters
and volatile acidity were performed according to the methods established by the Ministry of Agriculture,
Livestock and Supply. The results showed that the samples treated with clay adsorbed 3.6, 8.7, 9.4, 2.2
and 3.9% of the aldehydes, higher alcohols, furfural, esters, and volatile acidity, respectively. For the
samples treated with activated charcoal, the results were 6.5, 15.3, 95.31, 2.0 and 34.0% for the aldehydes,
higher alcohols, furfural, esters, and volatile acidity, respectively.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction Pecua ria e Abastecimento e MAPA), and the standards of quality

Distilled sugar cane spirits is a typical Brazilian beverage pro-
duced by the distillation of fermented sugar cane juice and is
widely marketed in the country, with an annual production of
about 1.5 billion liters (Cardoso, 2006). This volume is equivalent to
approximately 27% of the world production of distillates. According
to data from IBRAC (2010), 10.83 million liters were exported in
2009, generating revenues of US$ 15.58 million. The principal
markets include Germany, the USA, Portugal and France. However,
this volume is less than 1% of the total quantity of beverage
produced.
The quality of the beverage is inspected by the Ministry of
Agriculture, Livestock and Supply (Ministe rio da Agricultura,
* Corresponding author. Tel.: þ55 35 38291202; fax: þ55 35 38291271.
E-mail address: mcardoso@dqi.ufla.br (M.G. Cardoso).
are in accord with the norms required by Brazilian law (Brasil,
2005). Limits for organic and inorganic compounds are estab-
lished according to these norms. Copper, lead and arsenic are
among the inorganic contaminants. However, producers are very
concerned about the presence of copper since international law
establishes a limit (2 mg L
1) lower than that specified by Bra-
zilian legislation (5 mg L
1), and its presence is an obstacle to
exportation of the beverage (Cardoso, 2013). During the produc-
tion of the beverage, various steps and processes are applied. For
the spirit denominated cachaça, which is homemade or “artesa-
nal” and is produced mainly in the state of Minas Gerais, the
distillation process employs stills made of copper metal. These
stills are mainly responsible for the contamination of the
beverage. However, the use of these alambics yields beverages
with different aromas and flavors because this metal is active in
the catalysis of reactions of sulfides, which are compounds that
negatively affect the product.

http://dx.doi.org/10.1016/j.foodcont.2014.07.035
0956-7135/© 2014 Elsevier Ltd. All rights reserved.
 L.M. Zacaroni et al. / Food Control 47 (2015) 536e544
Copper is an essential metal for human metabolism because it
acts as a cofactor for several cellular enzymes such as catalase
(amineoxidase), cytochrome oxidase, dopamine b-hydroxylase, and
peroxidase (galactose oxidase). However, an excess of this metal
can cause serious diseases known as hypercupremia. At high con-
centrations, the metal may react with SH groups of proteins and
enzymes and is associated with diseases such as epilepsy, mela-
noma and rheumatoid arthritis, as well as the loss of the sense of
taste (Pedroso & Lima, 2001; Sargentelli, 1996).
Several alternatives have been used to reduce the excess copper
in cachaça. The most common practice, although contrary to the
legislation, is the commercialization of the product in the domestic
market without removing the copper ions or by blending the
distillate with other distillates containing a lower concentration of
this metal. Other methods for removing the copper involve the
inclusion of an adsorbent in the medium. These adsorbents are
generally functionalized synthetic materials of high adsorptive
capacity (Cantanhede, Lima, Lopes, Farias, & Bezerra, 2005). Several
studies have reported the use of these adsorbents and natural ad-
sorbents for the removal of copper ion from cachaça. Activated
charcoal, CaCO3, MgCO3, aluminosilicates and bentonite are among
the adsorbents studied (Bizelli, Ribeiro, & Novaes, 2000;
Cantanhede et al., 2005; Canta ~o, Melo, Cardoso, Anjos, & Oliveira,
2010; Lima, Cardoso, Guerreiro, & Pimentel, 2006; Neves,
Oliveira, Fernandes, & No  brega, 2007).
In recent years, special attention has been focused on the use
of natural resources as alternatives to conventional adsorbents.
Among the alternative adsorbents, clay stands out because of its
abundance and low cost compared to other adsorbents such as
activated charcoal, zeolites and synthetic ion exchange resins.
Moreover, clays are materials that can act as Lewis and Bro € nsted
acids and offer a large cation exchange capacity in a layered
structure that presents chemical and physical stability and a high
specific surface area (Chen, Hsiao, & Chen, 2008). This material
has been used in the environmental area for the removal of metals
(Cu2þ, Pb2þ, Cd2þ, Zn2þ, Ca2þ, Mg2þ, Mn2þ, Co2þ, Ni2þ) (Sanchez,
Ayuso, & Blas, 1999; Sari, Tuzen, Citak, & Soylak, 2007; Omer,
Altunkaynak, & Guzel, 2003; Veli & Alyus, 2007), organic com-
pounds (Abolino, Aceto, & Malandrino, 2003; Magriotis, Leal,
Sales, Papini, & Viana, 2010) and dyes (Nandi, Goswami, &
Purkait, 2009; Roulia & Vassiliadis, 2008; Vimonses, Jin, & Chow,
2010). It has also been used to control turbidity and chemical
products in the treatment of waste and as carriers of substances
such as pesticides, reducing leaching, volatilization and photo-
degradation (Gatica & Vidal, 2010). Given the above, the aim of
this study was to investigate the adsorption of copper by the clay
and activated charcoal matrix and evaluate the influence on the
quality of the beverage.
2. Material and methods
2.1. Adsorbate and adsorbent
Samples of clay used as adsorbent were collected from the
Indústria Higident in the municipality of Itajuba , MG. The samples
of distilled sugar cane spirits were collected in the southern region
of the state of Minas Gerais and forwarded to the Laboratory for
Physico-chemical Analysis of Distilled Sugar Cane Spirits, Federal
University of Lavras. Activated charcoal (Cromoline) was used for
comparison. The clay samples were homogenized and used directly
in experiments without pretreatment. The chemical composition of
the clay was determined using a Phillips model Cubix 3600 X-ray
fluorescence spectrometer (Almelo, Netherlands). The powder XRD
data were obtained in a Phillips spectrometer model PW 1710 using
Cu Ka1 radiation, scanning from 4 to 90 at a scan rate of 2q s
1.
537
The specific surface area was evaluated by means of adsorption and
desorption of nitrogen at 77 K using the method of Brunauer,
Emmett and Teller (BET) with a model ASAP 2020 Micromeritics
Analyzer (Dublin, Ireland). The Fourier transform infrared spectra
(FTIR) of adsorbents (in the form of KBr pellets) were measured
using a Digilab Excalibur FTS 3000 series spectrometer in the range
400e4000 cm
1 at a resolution of 4 cm
1. The morphology of the
samples was obtained by scanning electron microscopy (SEM) us-
ing a JEOL model JSM-5410 electron microscope (Tokyo, Japan).
Zeta potential was measured using a Zeta Meter 3.0þ, model ZM3-
D-G (Zeta Meter Inc.). The suspensions of the adsorbent, ground
before hand to less than 37 mm, were sedimented/conditioned at a
temperature of 22  C for 2 h, at the selected pH, in 250 mL
measuring cylinders with the addition of a 2  10
3 mol L
1 so-
lution of NaNO3, used as an indifferent electrolyte. The applied
tension varied in the range 75e200 mV. The average of 20 mea-
surements was taken as representing the measured potential.
2.2. The influence of physicochemical parameters on adsorption
The parameters evaluated in the study of adsorption were
contact time and the ratio of adsorbent to adsorbate. The effect of
pH on the process was not evaluated because this parameter is
fixed for the sugar cane spirits. Initially, the effect of contact time
between adsorbent and adsorbate at pH 5.5 (the natural pH of
cachaça) in the range from 15 min to 24 h was studied. The initial
copper concentration was 9.5 mg L
1, and a 1:100 ratio of mass of
adsorbent to volume of solution (g mL
1, corresponding to 0.6 g of
activated charcoal or clay and 60 mL of cachaça) was used. The
temperature was maintained at 298 K and the stirring speed at
140 rpm. In another experiment, the contact time was limited to the
15e180 min range for the clay and 15e1080 min for activated
charcoal, varying the ratio of adsorbent to volume of solution (1:50
and 1:500 g mL
1, corresponding to 1.2 g and 0.12 g of clay or
activated charcoal, respectively). After completing the contact pe-
riods, the samples were filtered by simple filtration, and the con-
centration of copper remaining in the cachaça was measured by
atomic absorption spectrophotometry (Varian model Spectr AA
110). All the assays were performed in triplicate. The percentage
removal was calculated using Eq. (1):
Co
Ct
%R ¼  100 (1)
Co
where Co is the initial copper concentration in the cachaça (mg L
1)
and Ct is the copper concentration at time t.
2.3. Adsorption isotherms
The adsorption isotherms for copper on clay and activated
charcoal were determined with the copper concentration at
0e2000 mg L
1, while the optimized parameters remained at their
optimum values. The amount of copper adsorbed per unit mass of
clay at equilibrium (Qe; mg g
1) was determined from Eq. (2):
ðCo
Ce ÞV
Qe¼ (2)
m
where Ce is the copper concentration (mg L
l) at equilibrium, m is
the mass of adsorbent (g) and V is the volume of solution. All the
experiments were performed in triplicate. The data were fitted to
the Langmuir isotherm (Hu & Sirinivasan, 1999):
Q m KL Ce
Qe¼ (3)
1 þ KL Ce
538 L.M. Zacaroni et al. / Food Control 47 (2015) 536e544

where Qm is the capacity for adsorption in a monolayer (mg g
1) established by the Ministry of Agriculture, Livestock and Supply
and KL (L mg
1) is the equilibrium constant of Langmuir and (Brasil, 2005).
of Freundlich (Nevskaia, Santines, Munoz, & Guerrero-Ruíz, 1999):
3. Results and discussion
1=nF
Q e ¼ KF Ce (4)
3.1. Characteristics of the clay
where KF is the Freundlich constant indicating the relationship for
the capacity for adsorption of the adsorvent (mg1
ð1=nF Þ L1=nF g
1 ), The chemical composition of the clay utilized is presented in
and 1=nF is the constant indicating the intensity of the adsorption. Table 1.
The X-ray spectrum of the clay is shown in Fig. 1. The clay
2.4. Adsorption kinetics contains a mixture of quartz and chlorite-vermiculite-
montmorillonite.
The adsorption kinetics of copper on clay and activated charcoal The surface charge of the adsorbent material in a certain pH
were investigated using previously optimized conditions. The first- value is determined by the measurement of the zeta potential, thus
order kinetics are represented by the model proposed by Lagergren permitting one to estimate whether the adsorption of cations or
(1898): anions is favored under certain conditions. According to Kubilay,
Gurkan, Savran, and Sahan (2007), Hþ ions will compete for bind-
dQ t ing sites on the surface and the net charge will be positive if the pH
¼ k1 ðQ e
Q t Þ (5)
dt of the solution is lower than the pHzpz. However, if the pH is higher
than the pHzpz of the material, the surface charge on the solid will
where Qe and Qt (mg g
1) are the adsorption capacities at equilib-
be negative. The zeta potentials of the activated carbon and clay
rium and at time t, respectively, k1 is the pseudo-first-order
used in this study are presented in Fig. 2.
(min
1), rate constant of adsorption. Integration of this equation
The activated charcoal was observed to possess a negative zeta
under the boundary conditions: t ¼ 0 at t ¼ t and Qt ¼ 0 at Qt ¼ Qt
potential at a pH above 3.11, so its surface has a high affinity for
produces Eq. (6) and Eq. (7):
cations at pHs above this value and for anions below pH 3.11. The
Qe negative zeta potential may arise from functional groups such as
ln ¼ k1 t (6) carboxylates and phenolic hydroxyl groups (Vieira, Magriotis,
Qe
Qt
Santos, Cardoso, & Saczk, 2012). When the pH used in the

adsorption process was equal to the pHzpz, i.e., equal to 3.11, the
Q t ¼ Q e 1
e
k1 t (7) surface of the activated charcoal was neutral.
The clay used in this work presented a negative zeta potential
The second order kinetics was represented by the model pro- for all the pH ranges studied, indicating that the solid had a high
posed by Ho and Mackay (Ho & Mckay, 1999): affinity for cations. This fact is interesting for the present study,
which evaluates the adsorption of copper (Cu2þ) in cachaça.
dQ t
¼ k2 ðQ e
Q t Þ2 (8) FTIR spectroscopy was used to analyze and identify the key
dt functional groups present in the structures of the clay and activated
carbon. The spectra are presented in Fig. 3.
Where Qe and Qt (mg g
1) are the adsorption capacities at equi-
An intense band located at 1040 cm
1, corresponding to the in-
librium and at time t, respectively; k2 is a pseudo-second-order
plane stretching of the SieO bond, can be observed in the spectrum
adsorption proportionality constant (mg g
1 min
1). Separating
presented in Fig. 3a. According Madejova  and Komadel (2001), this
the variables in Eq. (8) and integrating for the boundary conditions
band is characteristic of the SieO stretching vibration of cristoba-
of t ¼ 0 at t ¼ t and Qt ¼ 0 at Qt ¼ Qt yields Eq. (9):
lite. The spectrum of the clay sample also has a weak absorption at
1 1 3620 cm
1 that is related to the stretching vibration of the hydroxyl
¼ þ k2 t (9) groups located between the tetrahedral and octahedral layers of the
ðQ e
Q t Þ Q e
clay (Leite, Raposo, & Silva, 2008; Madejova , 2003). The presence of
This equation can be rearranged to yield Eq (10). water molecules adsorbed on the clay structure generated a band
around 3408 cm
1 related to the stretching of the HOH bond and
Q 2e k2 t another band near 1630 cm
1 corresponding to the bending vi-
Qt ¼ (10) bration of the HOH bond (Leite et al., 2008; Madejova , 2003). The
1 þ Q e k2 t
band at 800 cm
1 may be evidence for the presence of quartz and
silica. Another three bands located at 913, 536 and 467 cm
1
2.5. Analysis of congeners of cachaça correspond to deformations AleAleOH, AleOeSi and SieOeSi
deformations, respectively (Madejova  & Komadel, 2001).
The influence of adsorption on the concentration of congeners, Fig. 3b shows the FTIR spectrum of the activated charcoal. The
which are compounds responsible for flavor and aroma of the band centered in the 3436 cm
1 region indicated the presence of
beverage, was evaluated. For this purpose, the levels of aldehydes, hydroxyl groups. The absorption at 1631 cm
1 may correspond to
esters, furfural, higher alcohols' and volatile acidity before and after C]C stretching of the aromatic ring of lignin. The absorptions be-
the contact period were evaluated according to the parameters tween 1078 and 1037 cm
1 are due to the presence of CH2O groups
of phenols (Silverstein, Webster, & Kiemle, 2005) and can also
Table 1
confirm the presence of lignin in the material. These functional
Chemical composition of clay. groups may be potential sites for the adsorption of cations.
Fig. 3b shows the FTIR spectrum of the activated charcoal. The
Clay constituents SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O Loss on
ignition
band centered in the 3436 cm
1 region indicated the presence of
hydroxyl groups. The absorption at 1631e1560 cm
1 may corre-
Concentration (%) 53.76 14.41 6.78 1.07 1.17 0.10 1.57 15.00
spond to C]C stretching of the aromatic ring characteristic of
 L.M. Zacaroni et al. / Food Control 47 (2015) 536e544 539

Fig. 1. Powder XRD of clay.

20 carbonaceous material (Pereira, Oliveira, Vallone, Sapag, & Pereira,

Activated charcoal 2008). The absorptions between 1078 and 1037 cm
1 are due to the
Clay presence of CH2O groups of phenols (Silverstein et al., 2005). These
10
Zeta potential (mV)

functional groups may be potential sites for the adsorption of

pHzpz = 3.11 cations.
0 The adsorption/desorption isotherm of N2 at
196  C for clay
and activated charcoal is presented in Fig. 4.
-10 The profile of the adsorption/desorption isotherm for the clay
used in this work belongs to the type IV isotherm and is shown in
Fig. 4a. This type of isotherm is typical for mesoporous materials
-20
that may also contain micropores (Guerra, Airoldi, Lemos, Ange lica,
& Viana, 2008). The shape of the hysteresis shown in Fig. 4a in-
-30 dicates the presence of the typical slit-like pores of laminar parti-
cles with pores present between the blades. From the analysis of
-40 Fig. 4b, it can be said that the activated charcoal used in this study
0 2 4 6 8 10 12 14 also presented a type IV isotherm. The activated carbon presented
pH type B hysteresis, which is associated with long narrow pores and
indicated the presence of slit-shaped pores. In this type of pore, the
Fig. 2. Zeta potentials of clay and activated charcoal. adsorption occurs by the formation of multilayers, and the
desorption occurs by capillary evaporation. Lopes et al. (2013)
encountered the same profile for this isotherm in commercial
activated charcoal.

(a) 694 - 666

(b)
Transmitance (a.u.)

Transmitance (u.a.)

800
1631
3710
913
1630 3436
3620
536
3408
1118 1078 1037
467
1040
4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
-1 -1
Wavenumber (cm ) Wavenumber (cm )
Fig. 3. FTIR spectra of clay (a) and activated charcoal (b).
540 L.M. Zacaroni et al. / Food Control 47 (2015) 536e544

180 240
(a) (b)
160

Volume adsorbed (cm g )

230

-1

Volume adsorbed (cm g )

-1
140

3
220

3
120
100 210

80 200
60
190
40
adsorption 180 adsorption
20
desorption desorption
0 170
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
Relative pressure (P/P0) Relative pressure (P/P0)

Fig. 4. Nitrogen adsorption and desorption isotherms for clay (a) and activated charcoal (b).

The N2 adsorption data were treated according to the t-plot were, therefore, conducted for a maximum period of 120 min with
method (Lippens, Linsen, & Boer, 1964) and furnished values for the clay and 360 min with activated charcoal (Fig. 6).
external area (Aext), micropore volume (Vmicro) and mesopores The influence of the ratio of the amount of adsorbent to the
(Vmeso) of the solids studied. The pore diameter (Dp) was calculated amount of cachaça used on the removal of copper is shown in Fig. 7.
by the BJH method (Barrett, Joyner, & Halenda, 1951). The total pore When the value rose from 1:500 (0.12 g clay or activated charcoal
volume was calculated from the maximum volume adsorbed at P/ per mL) to 1:100 (0.60 g of clay or activated charcoal per mL), the
P0 ¼ relative pressure of 0.98. These data are presented in Table 2. efficiency of removal of copper increased from 45.3% to 82.5% for
The clay sample presented a larger mesoporous volume than the activated charcoal and from 45.0% to 68.7% for clay. However, the
activated carbon. This fact might favor the adsorption process. The
values obtained for Sext clay were also higher than those for the
activated carbon, as well as Dporo. These parameters can also
contribute to the adsorption process.
According to the literature, the surface area of activated charcoal
can range from 250 to 2500 m2 g
1, depending on the precursor
and the type of treatment used for the production of the activated
charcoal. However, the most common values are around
600e1000 m2 g
1 (Cabal et al., 2009; Hu & Sirinivasan, 1999;
Magriotis et al., 2010; Nevskaia et al., 1999; Olivares-Marín et al.,
2009). As for the clay, these values can vary from 10 to 45 m2 g
1
(Celi, Barberis, & Marsan, 2000; Celi, De Luca, & Barberis, 2005;
Cessa, Celi, Vitorino, Novelino, & Barberis, 2009; Jordi, Volker, &
Jiwchar, 2005; Magriotis et al., 2010). A higher value was ob-
tained for the clay sample analyzed.
Analyses by scanning electron microscopy were performed to
investigate the morphology of the adsorbents. The micrographs are
shown in Fig. 5. A heterogeneous grain size was observed in the clay
(Fig. 5A), and the porous structure of the activated charcoal can be
seen in Fig. 5B.

3.2. Influence of physico-chemical parameters on the adsorption of

copper by clay

An initial experiment regarding the influence of contact time

between adsorbate and adsorbent on the removal of copper by clay
and activated charcoal was conducted over a period of 1440 min
(24 h). The results showed that equilibrium was reached within
120 min for the clay, with removal of 68.7% of the copper, while the
equilibrium was reached at 360 min with activated charcoal and
82.5% of the copper was removed. All subsequent experiments

Table 2
Characterization of the texture of the clay and activated charcoal samples.

Adsorvent ABET Vmicro Vmeso VTotal Sext Dporo

(m2 g
1) (cm3 g
1) (cm3 g
1) (cm3 g
1) (m2 g
1) (Å)

Clay 174.00 0.045 0.201 0.246 123.75 74.70

Activated 643.36 0.289 0.067 0.356 45.06 37.45
charcoal
Fig. 5. SEM photomicrographs of clay (A) and pink (B) activated charcoal.
 L.M. Zacaroni et al. / Food Control 47 (2015) 536e544 541

100 12
Amount of copper adsorbed (%) Activated charcoal Clay

Qeq (mgadsorbg adsorvente)

10
80
8
60 Activated charcoal

-1
6
40
4

20 2

0 0
0 200 400 600 800 1000 1200 0 500 1000 -1
1500 2000
Ceq (mg L )
Time (min)
Fig. 8. Adsorption isotherms of copper on clay and activated charcoal.
100
Amount of copper adsorbed (%)

Clay
Table 3
80 Comparison between maximum capacities for adsorption of Cu2þin aqueous solu-
tion and cachaça by clay in various publications.

60 Adsorbent Metal Maximum Reference

adsorption
capacity
40 Qm (mg g
1)

Bentonite Cu2þ(cachaça) 90.0 Canta~o et al., 2010

20 Bentonite Cu2þ(aqueous) 10.8 Veli & Alyus, 2007
Na-montmorillonite Cu2þ(aqueous) 3.04 Abolino et al., 2003
Kaolinite (natural) Cu2þ(aqueous) 9.2 Abolino et al., 2003
0 Montmorillonite Cu2þ(aqueous) 10.1 Bhattacharyya
0 30 60 90 120 150 180 (natural) et al., 2011
Time (min) Kaolinite Cu2þ(aqueous) 31.8 Bhattacharyya
(acid-activated) et al., 2011
2þ
Fig. 6. Influence of contact time with clay and activated charcoal on the amount of Montmorillonite Cu (aqueous) 32.3 Bhattacharyya
copper adsorbed (%). (acid-activated) et al., 2011
Kaolinite Cu2þ(aqueous) 10.8 Omer et al., 2003

100 efficiency of removal amounted to 98.3% for the activated charcoal

Amount of copper adsorbed (%)

and remained unaltered for the clay when the 1:50 ratio (1.20 g of
80 clay or activated charcoal per mL) was used. Thus, the 1:50 ratio of
adsorbent to volume of solution was considered optimum for
60 adsorption. This percentage removal obtained for the clay reduced
the copper concentration from 9.5 to 3.0 mg L
1 in the beverage,
and this concentration is lower than that required by the Ministry
40
Activated charcoal of Agriculture, Livestock and Supply (Brasil, 2005).

20 1:50
1:100 3.3. Comparison of the isotherms for clay and activated charcoal
1:500
0
0 200 400 600 800 1000 1200 Tests were performed using the optimized parameters to
Time (min) compare the adsorption isotherms of activated charcoal and clay.
The adsorption capacity of clay for copper was higher than that of
100
activated charcoal (10.7 and 5.9 mg g
1, respectively) (Fig. 8). These
Amount of copper adsorbed (%)

results may be related to the clay composition compared to that of

80
the activated carbon and may possibly be due to the presence of
negative charges in this structure that are likely associated with
60

40 Table 4
Comparison between clay and charcoal adsorbents according to the Langmuir and
Clay Freundlich adsorption models.
20 1:50
1:100 Isotherm Parameters Clay Activated charcoal
1:500 Langmuir Qm 11.56 6.30
0
0 40 80 120 160 200 KL 0.0076 0.0074
R 0.8627 0.8796
Time (min)
Freundlich KF 1.4849 0.8385
nF 3.6395 3.7352
Fig. 7. Influence of the amount of adsorbent and solution volume (g mL
1) on the
R 0.9233 0.9211
amount of copper adsorbed (%).
542
1.0
Activated charcoal
0.8
Qeq (mgadsorbg adsorvente)
Clay
0.6
-1
0.4
0.2
0.0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Fig. 9. Influence of time on the values of Qt.
exchangeable cations (Table 1). Clay is normally used for the
removal of more polar substances, whereas charcoal has greater
affinity for non-polar substances.
The amounts of copper removed by the clay are within the
ranges reported in the literature for the removal of metal ions from
aqueous solution (10.83 mg g
1; Table 3). The percentage removal
of copper from cachaça by the clays used was lower than those
reported in the literature (Canta~o et al.,2010). According to Canta~o
et al. (2010), the differences observed in the adsorption of copper
from cachaça might be related to the chemical composition of the
beverage because the metal ions can be bound to bulky molecules
such as higher alcohols and their entry into the pores of the clay
would be reduced, resulting in a lower degree of adsorption of the
metal.
The results of the application of the nonlinear isothermal
models of Langmuir and Freundlich to the adsorption of copper
from cachaçha are shown in Table 4. The Langmuir isotherm has
been used for studies on the adsorption of metals and organic
compounds by clays (Chen et al., 2008; Magriotis et al., 2010; Vieira,
Almeida Neto, Gimenes, & Da Silva, 2010). It is based on simple
principles that include the uniform adsorption in a monolayer, a
finite number of active sites, an uniform energy of adsorption and
transmigration of the adsorbate on a level surface. However, the
Langmuir isotherm fails in that it assumes the independence of the
molecules and a uniform surface. The Freundlich isotherm, in an
attempt to overcome these deviations, assumes that adsorption
occurs on heterogeneous surfaces and considers the interaction
between the adsorbate molecules. As shown by the data presented
in Table 4 comparing the correlation coefficients (R), the Freundlich
isotherm was more suitable for explaining the adsorption of copper
by clay and activated charcoal. These results are similar to recent
work reported in the literature in which clay was used as an
adsorbent for cationic dyes in aqueous residues (Nandi et al., 2009;
Roulia & Vassiliadis, 2008) of copper (Sari et al., 2007; Veli & Alyus,
2007), lead (Sari et al., 2007) and zinc (Veli & Alyus, 2007).
Table 5
Comparison between adsorbents according to pseudo-first- and pseudo-second-
order kinetic models.
Model Clay

1
Experimental Qe (mg g ) 0.6108
Pseudo-first-order
k1 (min
1) 0.1118
Qe (mg g
1) 0.6150
R 0.9496
Pseudo-second-order
k1 (min
1) 0.4187
Qe (mg g
1) 0.6290
R 0.9713
L.M. Zacaroni et al. / Food Control 47 (2015) 536e544
3.4. Comparison between the types of kinetics of adsorption by clay
and activated charcoal
The Fig. 9 shows the analysis of data obtained from

1
Qt ðmgadsorbate gadsorbent Þ versus time (min).
The kinetic curves for adsorption are often useful for explaining
the mechanism of adsorption. The values for the pseudo-first order
and pseudo-second order kinetic models for the adsorption of
copper in cachaça are shown in Table 5. By comparing the corre-
lation coefficients (R), it can be seen that the removal of copper by
activated charcoal and clay is best described by pseudo-second-
order kinetics. These results are similar to those reported for the
adsorption of metals such as copper, iron, cobalt, zinc and nickel in
different matrices using clay as the adsorbent (Bhattacharyya et al.,
2008; Omer et al., 2003; Sari et al., 2007; Unuabonah, Adebowale, &
Dawodu, 2008; Veli & Alyus, 2007). The pseudo-second-order ki-
netic behavior indicates that the main type of mechanism that
controls the adsorption is the chemical reaction between the cop-
per ions and the functional groups present on the clay surface
(Moreira, Francisco, Oliveira, Nascimento, & Brito, 2009).
3.5. The influence of adsorption on the concentration of congeners
A problem reported by producers in the use of activated char-
coal for removal of copper from cachaça is the adsorption of similar
substances that are important for the flavor of the beverage. This
study sought to determine the effect of adsorbent on the removal of
these substances. According to the results presented in Fig. 10, the
concentrations of volatile acidity, aldehydes, esters, higher alcohols
and furfural, respectively, decreased by 34.0, 6.5, 2.0, 15.3 and 95.3%
relative to the control (cachaça with no adsorbent) when activated
charcoal was used. However, the concentrations of volatile acids,
aldehydes, esters, higher alcohols and furfural, respectively,
decreased by 3.9, 6.3, 2.2, 8.7 and 9.4% relative to the contole when
clay was used. These results demonstrate the specificity of clay in
removing the copper ions, without significant interference in the
concentrations of the congeners. Studies such as that of Lima et al.
(2006) show that, the longer the contact time and/or concentration
of charcoal used for the adsorption of copper, the more efficient the
removal of metal from the beverage. However, significant amounts
of secondary compounds are removed, depreciating the quality of
the beverage. Canta ~o et al. (2010) observed changes in the con-
centration of higher alcohols, aldehydes and esters when they
Activated charcoal
0.8007
0.0391
0.8036
0.8839
0.0732
0.8485
0.9630
Fig. 10. Removal of cachaça congeners using clay and activated charcoal.
 L.M. Zacaroni et al. / Food Control 47 (2015) 536e544
evaluated the adsorption capacity of aluminosilicates and clays. The
greatest reduction occurred with bentonite. In the case of higher
alcohols, bentonite promoted a 13.9% reduction compared to the
control, whereas zeolite contributed with a reduction of 21.6%. As
for the aldehydes, bentonite and zeolite promoted reductions of
7.8% and 3.4%, respectively. The reductions in the concentrations of
esters were 19.5% and 7.8% with bentonite and zeolite, respectively.
4. Conclusions
The adsorption of copper ions by activated charcoal and clay
occurred with equilibration times of 360 min and 120 min,
respectively, at pH 5.5. The ratio of adsorbent/volume of solution
employed was 1:50 at 140 rpm. The efficiencies of removal of
copper by activated charcoal and clay were 98.3% and 68.7%,
respectively. According to the adsorption isotherms, the values of
Qm obtained were 5.9 and 10.8 mg g
1 for charcoal and clay,
respectively. The Freundlich model was observed to best fit the
adsorption of copper by clay and activated charcoal. The adsorption
kinetics for the adsorption of copper by clay and activated charcoal
can be better explained by the pseudo-second-order model. A high
specificity of the clay in removing the copper ions with no signif-
icant reduction in the concentration of congeners was observed.
The results show that clay is an adsorbent suitable for removing
copper from cachaça, since this material is abundant and inex-
pensive and has appropriate physical and chemical properties.
Acknowledgments
The authors thank the Conselho Nacional de Desenvolvimento
 gico (CNPq, Grant No. 310795/2013-3) and the
Científico e Tecnolo
~o de Amparo e Pesquisa do Estado de Minas Gerais
Fundaça
(FAPEMIG, Grant No. PPM00418/3) for the scholarship granted and
for financial support, to the Coordenaça~o de Aperfeiçoamento de
Pessoal de Ensino Superior for a PVNS fellowship (D.L. Nelson,
Grant 06/2012) and the Chemistry Department of UFLA for support
of the analyses.
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