Instituto Tecnologico de Aguascalientes

From the SelectedWorks of Adrian Bonilla-Petriciolet

2013

Synthesis and adsorption properties of activated

carbons from biomass of Prunus domestica and
Jacaranda mimosifolia for the removal of heavy
metals and dyes from water
H. Treviño-Cordero
L.G. Juárez-Aguilar
D.I. Mendoza-Castillo
V. Hernandez-Montoya
A. Bonilla-Petriciolet, et al.

Available at: http://works.bepress.com/adrian_bonilla_petriciolet/270/

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Industrial Crops and Products 42 (2013) 315–323

Contents lists available at SciVerse ScienceDirect

Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

Synthesis and adsorption properties of activated carbons from biomass of Prunus

domestica and Jacaranda mimosifolia for the removal of heavy metals and dyes
from water
H. Treviño-Cordero a , L.G. Juárez-Aguilar a , D.I. Mendoza-Castillo a , V. Hernández-Montoya a ,
A. Bonilla-Petriciolet a,∗ , M.A. Montes-Morán b
a
Instituto Tecnológico de Aguascalientes, Aguascalientes, Mexico
b
Instituto Nacional del Carbón, INCAR-CSIC, Apartado 73, 33080 Oviedo, Spain

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

Article history: Activated carbon is the most widely used adsorbent for wastewater treatment and water pollution con-
Received 3 March 2012 trol. Lignocellulosic precursors obtained from crops and fruits offer several advantages for synthesizing
Received in revised form 21 May 2012 activated carbons due to its wide availability and their interesting physicochemical properties. In partic-
Accepted 24 May 2012
ular, biomass of plum kernel and jacaranda are alternative lignocellulosic precursors for activated carbon
preparation. This study reports the application of Prunus domestica and Jacaranda mimosifolia biomass for
Keywords:
the synthesis of activated carbons to remove commercial dyes (i.e., AB25 and methylene blue) and Pb2+
Activated carbon
ions from aqueous solutions. Two different methodologies for the preparation of activated carbons were
Heavy metals
Dyes
analyzed, namely, direct carbonization at 800 ◦ C and the impregnation of the biomass with a calcium
Jacaranda solution extracted from egg shell wastes prior to carbonization. Results indicated that both carboniza-
Plum kernels tion and activation processes improved the uptake of lead, acid blue 25 and methylene blue up to 10
Egg shells times with respect to adsorption results obtained for raw precursors. Characterization of raw precursors
and activated carbons by several techniques were used to understand the adsorption results obtained
in this study. Overall, activated carbons obtained from plum kernels showed the best performance for
the removal of these priority water pollutants. The adsorption capacities of plum kernel adsorbents are
higher (up to 100%) than those obtained for adsorbents prepared from jacaranda.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction 2009; Demirbas, 2009; Dias et al., 2008). It is important to recall

Activated carbons are applied in separation and purification
technologies, catalytic processes, biomedical developments, pollu-
tion control, and energy storage, among other usages. Specifically,
the use of activated carbon in wastewater treatment is nowadays
considered as an effective purification process for reducing trace
amounts of several pollutants to reach environmental standards
and regulations. The extensive application of activated carbon in
water treatment is mainly due to its relatively low-cost with respect
to other adsorbents, wide availability, high performance in adsorp-
tion processes and surface reactivity. This adsorbent offers good
versatility and flexibility to modify its physical and chemical prop-
erties, thus opening the possibility of preparing materials with
tailored characteristics (Haro et al., 2012). Until now, several types
of activated carbons have been used for the removal of priority pol-
lutants from water, especially heavy metals and dyes (Altenor et al.,
∗ Corresponding author. Tel.: +52 4499105002x127.
E-mail address: petriciolet@hotmail.com (A. Bonilla-Petriciolet).
that water pollution by both heavy metals and dyes is considered
as a serious environmental problem because these pollutants mod-
ify the chemical properties of water and are toxic to aquatic flora,
animals and human beings (Demirbas, 2008, 2009; Fu and Wang,
2011; Guezguez et al., 2009; Li et al., 2008). For example, heavy
metals are toxic even at relatively low concentrations while some
dyes may be carcinogenic. Based on these facts, the synthesis of
new activated carbons for water treatment is a current research
topic in the context of environmental pollution control.
Activated carbons used in wastewater treatment are tradition-
ally obtained from precursors such as wood, lignite and animal
bones (Altenor et al., 2009; Elizalde-González and Hernández-
Montoya, 2007; Mohamed et al., 2010). However, the interest for
the application of alternative and low-cost raw materials in the
production of this adsorbent has increased during last years. Lig-
nocellulosic biomass obtained from wastes and by-products of
crops and fruit production are considered as attractive precur-
sors for the preparation of activated carbons (Mohamed et al.,
2010). Activated carbons obtained from these precursors may
show physical, chemical and adsorption properties that may vary

0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2012.05.029
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316 H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323
significantly with respect to those properties of adsorbents
obtained from conventional raw materials (Tseng, 2007). Actually,
lignocellulosic residues from crops and fruit production can be
considered as the most appropriate precursors for a cost-effective
preparation of activated carbons based on the fact that several bil-
lion tons of these wastes are available worldwide (Mohamed et al.,
2010; Satyanarayan et al., 2007; Silvestre-Albero et al., 2012).
Similarly to other lignocellulosic materials, the basic chemi-
cal structure of crops and fruit residues comprises of cellulose,
hemicellulose and lignin (Mohamed et al., 2010). Thermo-chemical
processes are applied to synthesize activated carbons from these
materials and these adsorbents may show high porosity, usually
large surface area and high pore volumes. To date, a great variety
of lignocellulosic precursors and activating agents has been used
for the preparation of activated carbons for both heavy metal and
dye removal from water (Altenor et al., 2009; Demirbas, 2009).
In general, the precursors obtained from crops and fruit wastes
include chestnut shell, cane sugar bagasse, coconut shell, maize
talks, mango seed, guava seed, pecan nut shell, and coir pith,
among others (e.g., Chilton et al., 2003; Dastgheib and Rockstraw,
2001; Demirbas et al., 2009; Elizalde-González and Hernández-
Montoya, 2007, 2009a,b; Hernández-Montoya et al., 2011; Klasson
et al., 2009; Namasivayam and Sangeetha, 2006; Ozcimen and
Ersoy-Mericboyu, 2009; Tajar et al., 2009). As expected, the pre-
cursor composition may have a significant effect on the micropore
structure of the end product and, as a consequence, in the final
adsorption properties of activated carbons (Martinez et al., 2006).
On the other hand, different chemical activating agents can be used
for improving the adsorption properties of these carbons and they
include KOH, ZnCl2 , H2 SO4 , H3 PO4 and HNO3 . Alternatively, the
physical activation with CO2 and steam has been used. In particu-
lar, the chemical activation appears to be the most used procedure
for the preparation of adsorbents for water purification (e.g., Liu
et al., 2010; Namasivayam and Sangeetha, 2006). However, it is con-
venient to highlight that recent studies have reported that other
biomass and natural wastes (e.g., egg shell residues) can be used
as alternative and low-cost activating agents for improving the
adsorption properties of activated carbons used in water treat-
ment (e.g., Hernández-Montoya et al., 2011; Guijarro-Aldaco et al.,
2011). This approach offers additional advantages because it may
also contribute to significantly reduce the costs of activated carbon
production.
Particularly, biomass of plum kernel and jacaranda are alter-
native lignocellulosic precursors for activated carbon preparation.
Jacaranda is a flowering plant commonly found in America includ-
ing Mexico. The majority of jacaranda species are trees ranging
from 1 to 45 m tall (Gacher and Schuhly, 2009). Recent studies
have shown that this plant could have pharmacological potential in
the field of tropical diseases, skin problems and venereal illnesses
(Gacher and Schuhly, 2009). It appears that the biomass obtained
from the fruit of the specie Jacaranda mimosifolia has not been used
for the synthesis of activated carbons. On the other hand, the plum
is a temperate zone fruit crop, which is produced in Mexico and
other countries worldwide (Villegas Monter and Mora Aguilera,
2011). In the context of water treatment, the plum kernels have
been employed for preparation of activated carbon to remove dyes
and some heavy metal ions (e.g., Juang et al., 2000; Tseng, 2007;
Tseng et al., 2010; Wu et al., 1999). In general, these studies have
suggested that activated carbons prepared from plum kernels may
show good properties for adsorption in liquid phase. For example,
Wu et al. (1999) performed adsorption experiments of methylene
blue, basic red 22 and acid blue 25 on activated carbons obtained
from plum kernels. These activated carbons were prepared using
steam and different activation times and carbonization tempera-
tures. Afterward, Juang et al. (2000) studied the kinetics and the
adsorption mechanism at 30 ◦ C of the basic red and acid blue 25
commercial dyes using activated carbons obtained from plum ker-
nels. Recently, Tseng (2007) and Tseng et al. (2010) reported the
removal of acid blue 74, basic brown 1 and methylene blue using
activated carbons obtained from plum kernels by NaOH and steam
activation, respectively.
In this study, activated carbons for water treatment have been
prepared using biomass from jacaranda fruit and plum kernels. In
particular, the adsorption properties of both raw Prunus domes-
tica and Jacaranda mimosifolia biomass, and their activated carbons,
have been studied and compared in the removal of heavy metals
and dyes from aqueous solutions. This study analyzes the effect
of carbonization and activation processes, using a calcium solu-
tion extracted from egg shell wastes as activating agent, on the
adsorption properties and characteristics of these activated car-
bons. In general, results indicated that activated carbons obtained
from plum kernels showed the best adsorption capacities for the
removal of both dyes and heavy metals from water.
2. Methodology
2.1. Description of lignocellulosic precursors
Biomass obtained from plum kernel (PK) and jacaranda (JA)
were considered as precursors for activated carbon preparation.
The fruit of Jacaranda mimosifolia tree and the kernel of Prunus
domestica plum were collected in Aguascalientes (Mexico). This
biomass was grounded and sieved to obtain a particle size of 1 mm.
They were washed using deionized water at 25 ◦ C until pH was
constant to remove soluble impurities and, finally, they were dried
at 70 ◦ C for 24 h. These raw materials were stored in a desicca-
tor for later use in both adsorption experiments and preparation
of activated carbons. Chemical and physical properties of these
raw materials were established according to the procedures given
below.
2.2. Preparation of activated carbons
Two types of carbons were prepared in this study: the first
carbon was obtained by single carbonization of the raw precur-
sor (i.e., jacaranda fruit or plum kernels) and the second carbon
type was prepared by impregnation of these precursors with a
calcium solution (25%v) extracted from egg shells, using H3 PO4
(1 M) for the precursor pretreatment, finally, the impregnated
precursors were carbonized. Details for the precursor impreg-
nation are given elsewhere (Hernández-Montoya et al., 2011).
Briefly, acetic acid (25%v) was used to prepare the calcium solu-
tion from the egg shell wastes employing a mass to volume ratio
of 50 g of egg shells per liter of acetic acid. It is convenient to
remark that this solution has a significant content of calcium (i.e.,
12,604 mg/L), because the egg shell contains up to 95% of CaCO3 .
Previous studies showed that this calcium solution can be used
as activating agent for improving carbon adsorption properties
because this cation may play an important role in the removal
of heavy metals and other water pollutants (e.g., Guijarro-Aldaco
et al., 2011; Hernández-Montoya et al., 2011). Therefore, this study
introduces the application of egg shell wastes for the prepara-
tion of activated carbons using biomass of jacaranda fruit and
plum kernels. In particular, the effect of this activating agent on
the adsorption properties of activated carbons obtained from both
precursors has been analyzed.The carbonization process was per-
formed with a horizontal tubular furnace Carbolite Eurotherm
model CTF 12,165/550 with a quartz reactor. Samples (i.e., 30 g)
were heated from room temperature to 800 ◦ C in the atmosphere
of the products released as a result of the carbonization. The tem-
perature program comprised two heating ramps: (1) from room
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H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323 317

temperature to 70 ◦ C with 5 ◦ C min−1 and a residence time of 1 h, (2) Table 1

Elemental composition of the raw precursors and activated carbons obtained from
from 70 to 800 ◦ C with 5 ◦ C min−1 and a residence time of 4 h. Note
jacaranda and plum kernels.
that this carbonization temperature was established using prelimi-
nary results of adsorption experiments (not reported in this paper). Element (%) Precursor Carbons Precursor Carbons
In particular, previous studies and the results reported in the JA CJ CI-J PK CP CI-P
literature (e.g., Figueiredo et al., 1999; Faria et al., 2004; Elizalde-
C 48.2 95.81 80.97 52.0 94.82 86.08
González and Hernández-Montoya, 2009c) indicate that the H 4.4 0.75 0.67 6.20 0.79 0.64
decomposition of some functional groups of activated carbons N 0.2 0.0 0.0 0.3 0.0 0.0
obtained from lignocellulosic precursors occurs at high tempera- S 0.0 0.36 0.35 0.0 0.40 0.38
O 47.2 3.60 6.61 45.2 3.94 5.27
tures, but the specific surface area increases with the carbonization
temperature. In this study, some carbon samples were obtained at
different carbonization temperatures but the samples prepared at adsorption experiments were conducted in duplicate at batch
800 ◦ C were the more effective for the removal of dyes and heavy conditions and average results are reported in this study. Repro-
metals (results not reported in this paper). Based on this fact, the ducibility of the experiments was very high and in general <5%.
carbonization temperature was set at 800 ◦ C in this study. Carbon Dye concentration was determined by UV–vis spectrometry at the
samples obtained from carbonization of biomass of jacaranda fruit maximum absorbance of AB25 (i.e., 600 nm) and MB (i.e., 661 nm)
and plum kernel were labeled as CJ and CP, respectively, while using an UV–vis HACH DR 5000 spectrophotometer. On the other
activated carbons obtained from the calcium-impregnation were hand, concentrations of Pb2+ were determined with a Perkin Elmer
assigned as CI-J and CI-P. AAnalist 100 atomic absorption spectrophotometer equipped with
an air-acetylene burner.
2.3. Characterization of raw precursors and activated carbons Adsorption capacities for Pb2+ , AB25 and MB (qi , mg/g) of all
adsorbents (i.e., raw and carbon materials) were calculated by a
The content of carbon, hydrogen, nitrogen and sulfur in the raw mass balance
precursors and carbon adsorbents was determined using a LECO (C0,i − Cf,i )V
CHNS-932 elemental analyzer and the oxygen content with a LECO qi = (1)
m
VTF-900. SEM/EDX analyses were performed with a FE-SEM system
where C0,i and Cf,i is the initial and final concentration (mg/L) of
(Quanta FEG 650, FEI). Solid particles were dispersed on a graphite
pollutant i (i.e., dye or heavy metal) in the solution, V is the volume
adhesive tab placed on an aluminium stub. No further coating was
(L) of pollutant solution used for adsorption experiments and m
required and a semi-quantitative analysis of the principal elements
is the adsorbent amount (g), respectively. An analysis of variance
was performed by integration of the peaks identified by EDX.
(ANOVA) has been performed to compare the maximum adsorption
The textural parameters of activated carbons were calculated
capacities obtained for all adsorbents.
from the adsorption isotherms of nitrogen at −196 ◦ C. An auto-
mated adsorption apparatus (Micromeritics ASAP 2420) was used.
3. Results and discussion
The experimental points of the nitrogen isotherms were analyzed
using suitable methods for microporous materials. On the other
3.1. Characterization of precursors and activated carbons
hand, the specific surface area of the raw precursors was calcu-
lated from the adsorption isotherms of methylene blue at 30 ◦ C
3.1.1. Raw precursors
according to the methodology reported by Elizalde-González and
The jacaranda fruit and plum kernel are mainly constituted
Hernández-Montoya (2007). Finally, the acidity and basicity of all
by carbon and oxygen (see Table 1). They show an elemental
adsorbents were quantified by potentiometric titration according
composition very similar to those reported for other lignocellu-
to the study reported by Faria et al. (2004). In these quantifications,
losic materials such as pecan nut shells (C: 52.2% and O: 40.5%),
an Oakton pH meter was employed during continuous deaeration
cherry stones (C: 51.80% and O: 41.60%), Brazil nut shells (C:
with nitrogen.
50.0%, O: 43.5%), or the husk of the mango pit (C: 50.0%, O: 43.5%)
(Bonelli et al., 2001; Durán-Valle et al., 2005; Hernández-Montoya
2.4. Adsorption experiments of heavy metals and dyes et al., 2011). A statistical analysis of element composition using
mass units was performed and results indicate that the differ-
Adsorption isotherms of lead (Pb2+ ), acid blue 25 (AB25) and ence of composition of both precursors is statistically significant
methylene blue (MB) were obtained using raw precursors and (p-level < 0.05). According to their nature, cellulose, hemicellulose
carbonaceous adsorbents (i.e., CJ, CP, CI-J and CI-P). These adsorp- and lignin should be the principal components of JA and PK. Both
tion isotherms were used to determine the maximum adsorption JA and PK have an acidic character showing a total acidity of 1.14
capacities of all adsorbents. Batch adsorption experiments were and 1.02 mmol/g, respectively, which is mainly due to the pres-
performed using pollutant solutions with different initial concen- ence of oxygenated groups such as carboxylic and phenolic in these
trations. In particular, initial concentrations ranged from 50 to materials. On the other hand, the basicity of these materials is very
1500 mg/L for AB25 and MB and from 20 to 250 mg/L for Pb2+ . low (∼0.3 mmol/g) as reported for other wastes such as manso-
Metal solutions were prepared from Pb2+ nitrate (J.T. Baker) and nia wood sawdust and avocado kernel (Elizalde-González et al.,
deionized water, while dye solutions were prepared from AB25 2007; Ofomaja, 2011). The specific surface area of JA (33 m2 /g) is
(Sigma–Aldrich), MB (Sigma–Aldrich) and also deionized water. higher than that of PK (23 m2 /g), as determined from the methy-
All chemicals were of analytical grade. Adsorption studies were lene blue adsorption isotherms. These values also lie in the range
performed by shaking a fixed mass of adsorbent (from 0.01 to of results reported for other lignocellulosic materials and are lower
0.02 g depending on the pollutant under study) in fixed volumes than those obtained for activated carbons (Elizalde-González et al.,
of pollutant solution (10 mL) at 30 ◦ C, for 24 h to reach the adsorp- 2007; Elizalde-González and Hernández-Montoya, 2007).
tion equilibrium, using a temperature-controlled shaker operated
at 200 rpm. These experiments were performed at pH 6 for AB25 3.1.2. Activated carbons
and MB, and pH 5 for Pb2+ . Note that pH is below the onset for The elemental composition of activated carbons obtained from
hydrolysis of Pb2+ in order to prevent metal precipitation. All the JA and PK is reported in Table 1. A notable difference in the carbon
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318 H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323

Fig. 1. SEM images of the carbons obtained by single carbonization of plum kernel (a) and jacaranda (c) and by impregnation of plum kernel (b) and jacaranda (d) with
H3 PO4 + Ca.

content of the samples obtained by carbonization (CJ and CP) or by Table 2

Principal elements identified on the adsorbent surface by SEM/EDX at 20 ␮m.
impregnation plus carbonization (CI-J and CI-P) of the two precur-
sors is observed and this composition difference was statistically Element CJ (% ± SD) CI-J (% ± SD) CP (% ± SD) CI-P (% ± SD)
significant (p-level < 0.01). The reduction in carbon content of the C 100 ± 0 82.49 ± 6.0 100 ± 0 70.77 ± 1.34
CI-J and CI-P is most likely related to the remains of the calcium O – 9.40 ± 2.0 – 13.69 ± 2.00
salts used as activating agent. Thus, significant quantities of Ca and Ca – 4.75 ± 1.5 – 9.77 ± 0.49
P were observed on the surface of CI-J and CI-P by EDX analysis P – 3.35 ± 0.82 – 5.76 ± 2.30

(see Table 2). The distribution of these two elements on the CI-J SD: standard deviation obtained from three determinations.
and CI-P surfaces is mainly located at the brighter spots of the SEM
micrographs shown in Fig. 1. These spots are only observed in the
images corresponding to the carbons obtained by the impregnation

Table 3
Textural parameters obtained from adsorption isotherms of nitrogen at 77 K of the carbon samples with and without calcium impregnation.

Sample Textural properties

SBET (m2 /g)a Vt (cm3 /g)b VDRN2 (cm3 /g)c VMESO (cm3 /g)d Micro (%)e

CI-P 329 0.155 0.135 0.025 87

CI-J 326 0.152 0.134 0.024 86
CP 417 0.204 0.193 0.011 95
CJ 235 0.110 0.098 0.012 89
a
BET surface area.
b
Total N2 pore volume (at p/p0 = 0.98).
c
Micropore volume obtained by applying the Dubinin–Raduskevich (DR) equation.
d
Mesopore volume = total N2 pore volume Vt (at p/p0 = 0.98) − VDRN2 .
e
% of micropore volume (VDRN2 ) over the total N2 pore volume Vt (at p/p0 = 0.98).
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H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323 319

7.2 6.0

5.4 4.5

qe for Pb2+, mg/g

3.6 3.0

1.8 1.5

0.0 0.0
0 60 120 180 240 0 60 120 180 240

60 52

45 39
qe for AB25, mg/g

30 26

15 13

0 0
0 360 720 1080 1440 0 360 720 1080 1440
240 120

180 90
qe for MB, mg/g

120 60

60 30

0 0
0 340 680 1020 1360 0 340 680 1020 1360
Ce, mg/L Ce, mg/L
a) Plum kernels b) Jacaranda fruit

Fig. 2. Adsorption isotherms of Pb2+ , AB25 and MB at 30 ◦ C using () raw precursor, () carbon and () calcium-impregnated carbon.

procedure, i.e., Fig. 1b and d. It is convenient to remark that the
size of the inorganic salts could be small enough as for clogging
the porosity of the samples. This could be the case of the CI-P car-
bon. The occurrence of these inorganic salts on the surface of CI-P
could then explain its lower pore volume and surface area when it
is compared to that of CP (Table 3). Table 3 also indicates that the
development of porosity during the carbonization is more effec-
tive in the case of the plum kernel precursor (CP carbon) than in
the jacaranda biomass (CJ carbon). The difference in % of microp-
ore volume of CP and CJ was statistically significant (p-level < 0.01),
while CI-P, CI-J and CJ showed practically the same porosity (p-
level > 0.05). As evidenced by SEM, the morphology of the two
carbons is very different (Fig. 1a and c). For the jacaranda precur-
sor, the addition of the activating agent would promote a more
developed porous texture thus bringing about carbons (CI-J) with
higher pore volumes and surface areas than the only-carbonized
counterparts (CJ). In this case, it also seems that the development
of the porosity would overcome the possibility of pore clogging
by the calcium salts. Nevertheless, CI-J and CI-P show very similar
textural properties (see Table 3).
3.2. Adsorption isotherms of Pb2+ , AB25 and MB
Fig. 2 shows the adsorption isotherms of Pb2+ , MB and AB25
at 30 ◦ C using the raw precursors and the carbon adsorbents pre-
pared by the two routes described in the experimental section.
These isotherms can be classified as L-2 type according to the
classification suggested by Giles et al. (1974), which indicate a
favorable adsorption process. Results point out that all pollutants
were adsorbed in a greater extent on the carbon samples than on
the raw precursors. Overall, the adsorption capacities may increase
up to 10 times after the carbonization of the raw precursors. In
particular, the increment of adsorption properties is more signifi-
cant for MB and AB25. For example, the adsorbed amounts of MB
and AB25 increased from 27.1 ± 0.09 to 81.0 ± 0.08 mg/g and from
7.7 ± 0.05 to 43.2 ± 0.01 mg/g, respectively, using jacaranda fruit
and the CJ sample. On the other hand, the use of jacaranda and plum
kernel biomass as biosorbents might be considered for the adsorp-
tion of Pb2+ . For this particular pollutant, jacaranda fruit performs
better than the plum kernels. This better performance is possibly
due to the higher surface area of the JA compared to PK, as quoted
above. Actually, Pb2+ removal seems to be mainly determined by
the textural properties for the adsorbents. Hence, the highest Pb2+
retention capacities on all adsorbents tested have been obtained for
the CP sample, which shows the highest total pore and micropore
volumes of all carbons tested (see Table 3).
With the exception of Pb2+ on CP discussed already, the adsorp-
tion capacities of the carbonized-only precursors could be further
improved using the calcium impregnation of the biomass prior
carbonization. In the case of Pb2+ adsorption on the jacaranda
fruit-derived carbons, the use of the activating calcium solution
is effective because of an improvement of the textural properties
of CI-J is attained when compared to CJ. For the adsorption of dyes,
the capacities of CI-J and CI-P are higher than those obtained using
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320 H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323

Fig. 3. Maximum adsorption capacity of raw precursors and activated carbons obtained from (a) plum kernels and (b) jacaranda fruit for the removal of water pollutants.
Adsorbents: () raw precursor, (#) carbon without calcium impregnation, and () carbon with calcium impregnation.

CJ and CP for the removal of AB25 and MB (see Fig. 2). Overall, approach (Guijarro-Aldaco et al., 2011). This topic will be consid-
dye uptakes may increase up to 75% if the precursors are treated ered for further studies of these adsorbents. On the other hand, the
with the calcium solution. It appear that the effect of this activat- removal performance of CI-P and CI-J appears to be promising with
ing agent (i.e., calcium solution extracted from egg shells) on the respect to results reported for commercial activated carbons such
adsorption properties may depend on the precursor type and the as carbon F-400. Finally, as stated in the introduction, some stud-
pollutant to be removed. Microporosity seems to play a secondary ies have reported the synthesis of activated carbons obtained from
role in the adsorption process of the tested dyes, which would be plum kernels and its application for dye removal including AB25
eventually caused by the size of the adsorbed molecules and the and MB (e.g., Juang et al., 2000; Tseng, 2007; Tseng et al., 2010;
chemistry of the carbon surfaces. So, the adsorption of AB25 and MB Wu et al., 1999). These authors have reported that these activated
on the CI-P is always higher than that on CP, in spite of the excellent carbons may show adsorption capacities from 100 to 500 mg/g for
textural parameters of this latter carbon. Similarly, impregnated both AB25 and MB. Even though a proper comparison of the adsorp-
plus carbonized plum kernels always led to carbons with superior tion capacities of other adsorbents with respect to results obtained
adsorption properties when compared to CI-J samples, regardless in this study is not completely possible due to the broad diver-
the similar textural properties of the CI-J and CI-P carbons. Nev- sity of experimental conditions used (e.g., adsorbent particle size,
ertheless, it seems that the presence of the calcium salts on the pH), results of Fig. 3 and Table 4 suggest that activated carbons
surfaces of those carbons is determinant in obtaining a significant obtained from both plum kernels and jacaranda biomass, and using
increment of their dye retention ability. In summary, maximum the impregnation with calcium solution, show competitive adsorp-
adsorption capacities for all pollutants and adsorbents are reported tion capacities for the removal of Pb2+ , AB25 and MB. Furthermore,
in Fig. 3. ANOVA analysis confirmed that the differences observed the approach detailed in this paper to obtain activated carbons for
for maximum adsorption capacities of carbon samples were statis- wastewater treatment offers a possibility to reduce the cost of their
tically significant (p-level = 0.03). The adsorbed amount of MB on production, considering that the reuse of egg shell wastes as acti-
the different activated carbons was in general higher than those vating agent for carbon synthesis is attractive from the viewpoint
obtained for AB25 and Pb2+ . Specifically, results indicate that the of the waste recycle and minimization of pollutants.
adsorption capacities were found to follow the sequence: car- Langmuir, Freundlich and Sips models have been used to fit
bon obtained from calcium impregnation of precursors > carbon adsorption isotherms. In first instance, Langmuir model assumes
obtained from raw precursors > raw precursors. Statistical analy- that adsorption occurs in a monolayer where the active sites are
sis confirmed this result and the standard deviations of adsorption
capacities ranged from 0.01 to 0.25 mg/g for PK, CP and CI-P, and Table 4
from 0.01 to 0.14 mg/g for JA, CJ and CI-J, respectively. Adsorption capacities of AB25, MB and Pb2+ for several adsorbents reported in
With illustrative purposes, Table 4 contains the adsorption literature.
capacities of AB25, MB and Pb2+ for several adsorbents reported Pollutant Adsorbent Adsorption Reference
in literature including commercial activated carbons (e.g., carbon capacity, mg/g
F-400). It is convenient to remark that the adsorption capacities
Pb2+ Carbon nanotubes 12.41 Yan-Hui et al. (2005)
of calcium-impregnated carbons are higher than those reported Bentonite 15.38 Bereket et al. (1997)
for other adsorbents. For example, the AB25 and MB adsorption Modified coconut shell 29.44 Goel et al. (2005)
capacities of CI-P (i.e., 206.6 and 58.9 mg/g) are higher than those activated carbon
Oak wood char 2.62 Mohan et al. (2007)
reported for peat: 12.7 mg/g of AB25 (Ho and McKay, 1998), saw-
Oak bark char 13.1 Mohan et al. (2007)
dust: 24.4 mg/g of AB25 (Hanafiah et al., 2012), bentonite: 151 mg/g Carbon F-400 30.12 Mohan et al. (2007)
of MB (Hong et al., 2009), and bamboo dust activated carbon: AB25 Peat 12.7 Ho and McKay (1998)
143.2 mg/g of MB (Kannan and Sundaram, 2001). For the case of Diatomite 21.0 Badii et al. (2010)
Pb2+ removal, the adsorption capacity of CP is higher than those Sawdust 24.4 Hanafiah et al. (2012)
Activated carbon 48.0 Hernández-Montoya
obtained for some chars (Mohan et al., 2007) and is relatively lower
obtained from pericarp et al. (2011)
than those reported for other adsorbents such as bentonite (Bereket of pecan
et al., 1997) and carbon nanotubes (Yan-Hui et al., 2005). It is MB Carbon F-400 476 El Qada et al. (2008)
important to remark that the adsorption properties of these acti- Bamboo dust activated 143.2 Kannan and Sundaram
vated carbons can be improved if an optimization of the synthesis carbon (2001)
Bentonite 151 Hong et al. (2009)
operating conditions is performed using, for example, the Taguchi
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H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323 321

0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0
Raw precursor 32 9.2 20 8.0 28 8.0

24 6.9 15 6.0 21 6.0

16 4.6 10 4.0 14 4.0

8 2.3 5 2.0 7 2.0

0 0.0 0 0.0 0 0.0

Experimental adsorption capacity, mg/g

0 7 14 21 28 0 7 14 21 28 0 7 14 21 28
0.0 1.9 3.8 5.7 7.6 0.0 1.8 3.6 5.4 7.2 0.0 1.8 3.6 5.4 7.2
160 8.4 140 7.2 124 8.0

120 6.3 105 5.4 93 6.0

Carbon

80 4.2 70 3.6 62 4.0

40 2.1 35 1.8 31 2.0

0 0.0 0 0.0 0 0.0

0 30 60 90 120 0 30 60 90 120 0 30 60 90 120
0.0 1.4 2.8 4.2 5.6 0.0 1.4 2.8 4.2 5.6 0.0 1.4 2.8 4.2 5.6
268 7.2 244 6.8 240 5.6
Calcium-impregnated

201 5.4 183 5.1 180 4.2

carbon

134 3.6 122 3.4 120 2.8

67 1.8 61 1.7 60 1.4

0 0.0 0 0.0 0 0.0

0 55 110 165 220 0 53 106 159 212 0 53 106 159 212
Freundlich Langmuir Sips
Calculated adsorption capacity, mg/g

Fig. 4. Comparison of experimental and calculated adsorption capacities of Pb2+ (♦), MB () and AB25 () using raw precursors and activated carbons. Plum kernels (♦, ,
) and Jacaranda fruit (♦, , ).

identical and energetically equivalent (Langmuir, 1918; Liu and Liu, The adjustable parameters of these isotherms that provide the
2008). This isotherm is given by best fit to measured adsorption data were determined using a
non-linear regression approach. In particular, the determination of
qm KCe model parameters for adsorption isotherms is based on the global
qe = (2)
1 + KCe minimization of the following objective function
where qe and Ce are the pollutant uptake (mg/g) and concentration ndat 
 2
(mg/L) at equilibrium, qm is the theoretical maximum adsorption qi,exp − qi,calc
Fobj = (5)
capacity (mg/g), and K (L/mg) represents the Langmuir equilibrium qi,exp
i=1
constant, respectively. Both qm and K are obtained from adsorption
data correlation. Alternatively, Freundlich model is an empirical where qi,exp and qi,calc are the experimental and predicted adsorp-
expression used to describe a heterogeneous system (Freundlich, tion capacities and ndat is the overall number of experimental data,
1096; Liu and Liu, 2008), which is defined as respectively. In this study, a stochastic global optimization method
(i.e., Simulated Annealing) was used to determine the model
1/n
qe = Kf Ce (3) parameters of isotherm equations. According to results obtained
in previous studies (e.g., Guijarro-Aldaco et al., 2011; Hernández-
where Kf (mg1−1/n L1/n g−1 ) and n are parameters characteristic of Montoya et al., 2011), this non-linear regression approach using the
the adsorbent–sorbate system, which must be determined by data simulated annealing method is reliable and suitable for adsorption
fitting. Finally, Sips isotherm is a model that incorporates the fea- data modeling. Finally, the next statistical criterions were used to
tures of both Langmuir and Freundlich models (Liu and Liu, 2008; identify the best isotherm equation for modeling adsorption data:
Sips, 1948). At low concentrations, the Sips model reduces to the the correlation coefficient (R2 ), the objective function value (Fobj )
Freundlich isotherm while, at higher concentrations, it may pre- and the mean absolute percentage deviation (E) between calculated
dict a monolayer adsorption capacity characteristic of the Langmuir and experimental adsorption data, where
isotherm. Specifically, this model is given by
 
100   qi,exp − qi,calc 
ndat
qs as Cens E= (6)
qe = (4) ndat  qi,exp 
1 + as Cens i=1

where qs is the theoretical maximum adsorption capacity (mg/g), These statistics were accompanied by a study of the behavior
as and ns are the Sips parameters. As stated in our previous studies of the relative residuals ei = qi,exp − qi,calc /qi,exp to identify obvious
(e.g., Aguayo-Villarreal et al., 2011), the parameter ns was consid- patterns of adsorption isotherm models.
ered as an empirical adjustable parameter (i.e., no restrictions were Results of isotherm data modeling are reported in Fig. 4 and
imposed for its values during data fitting) given that this isotherm Tables 5 and 6. In particular, Fig. 4 compares the experimental and
is empirical and ns has no clearly defined physical meaning. predicted adsorption capacities using Langmuir, Freundlich and
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322 H. Treviño-Cordero et al. / Industrial Crops and Products 42 (2013) 315–323

Table 5
Results of adsorption data modeling using Langmuir, Freundlich and Sips isotherm models.

Pollutant Model Plum kernels Jacaranda fruit

Raw precursor CP CI-P Raw precursor CJ CI-J

Pb2+ Freundlich R2 0.844 0.903 0.521 0.973 0.772 0.742

Fobj 0.131 0.064 0.201 0.058 0.483 0.353
Eabs 9.61 ± 6.53 6.43 ± 4.99 11.45 ± 8.82 6.94 ± 3.25 22.03 ± 7.60 18.04 ± 8.61
Langmuir R2 0.967 0.963 0.793 0.978 0.843 0.890
Fobj 0.022 0.038 0.087 0.104 0.505 0.944
Eabs 3.63 ± 3.13 5.53 ± 2.89 7.10 ± 6.40 7.73 ± 7.01 21.01 ± 11.60 12.48 ± 6.90
Sips R2 0.978 0.957 0.978 0.974 0.980 0.989
Fobj 0.015 0.032 0.006 0.061 0.036 0.012
Eabs 3.02 ± 2.58 4.69 ± 4.21 2.18 ± 1.32 7.11 ± 3.48 5.33 ± 3.63 2.97 ± 2.139
MB Freundlich R2 0.886 0.794 0.224 0.970 0.888 0.670
Fobj 0.250 0.616 1.899 0.180 0.500 2.078
Eabs 15.85 ± 11.13 24.48 ± 13.96 42.61 ± 25.25 13.63 ± 9.13 19.91 ± 19.24 43.05 ± 22.62
Langmuir R2 0.959 0.867 0.482 0.808 0.474 –
Fobj 0.283 0.596 1.579 0.535 1.002 –
Eabs 14.21 ± 15.34 22.41 ± 16.65 37.26 ± 25.87 24.91 ± 12.98 33.37 ± 19.27 –
Sips R2 0.980 0.987 0.819 0.986 0.887 0.859
Fobj 0.084 0.099 0.955 0.040 0.501 1.852
Eabs 9.29 ± 6.33 8.46 ± 0.98 28.02 ± 6.36 5.59 ± 5.44 19.99 ± 19.22 33.58 ± 32.26
AB25 Freundlich R2 0.768 0.786 0.963 0.876 0.975 0.990
Fobj 0.371 1.531 0.284 0.479 0.260 0.231
Eabs 18.84 ± 14.30 35.20 ± 22.82 15.82 ± 8.58 20.78 ± 17.16 14.44 ± 9.51 12.39 ± 10.76
Langmuir R2 0.869 0.891 0.979 0.910 0.980 0.996
Fobj 0.177 1.382 0.288 0.310 0.750 0.302
Eabs 12.29 ± 10.86 31.73 ± 24.43 13.93 ± 11.88 15.57 ± 15.26 19.63 ± 22.44 12.05 ± 14.63
Sips R2 0.861 0.972 0.977 0.923 0.975 0.994
Fobj 0.176 0.551 0.372 0.304 0.269 0.228
Eabs 12.68 ± 10.28 17.63 ± 18.43 14.21 ± 15.44 13.90 ± 16.78 14.56 ± 9.91 11.98 ± 11.13

Table 6
Parameters of Sips isotherm for modeling adsorption data of Pb2+ , MB and AB25 using raw precursors and activated carbons obtained from plum kernels and jacaranda fruit.

Pollutant Parameter Plum kernels Jacaranda fruit

Raw precursor CP CI-P Raw precursor CJ CI-J

2+
Pb qs , mg/g 2.229 11.093 2.058 47.571 4.574 6.146
a 0.012 0.024 0.000 0.001 3 × 10−4 0.001
n 1.193 0.828 3.022 0.811 1.864 1.718
MB qs , mg/g 24.056 146.737 241.878 34.240 5081.889 74.936
a 0.053 1 × 10−4 1 × 10−4 0.118 0.002 3 × 10−5
n 0.627 1.484 1.965 0.482 0.312 1.774
AB25 qs , mg/g 5.354 54.169 91.380 7.507 785.679 238.775
a 0.030 1 × 10−4 3 × 10−4 0.040 0.001 0.001
n 1.066 1.608 1.150 0.859 0.568 0.786

Sips isotherms for all adsorbents and pollutants. It is clear that
Sips isotherm generally gave better fits than Langmuir and Fre-
undlich isotherms for modeling adsorption data of all pollutants
and adsorbents tested. In general, the performance of the isotherm
equations for the adsorption data modeling of Pb2+ , AB25 and MB
is given by: Sips > Langmuir > Freundlich. Specifically, the values of
R2 ranged from 0.86 to 0.99 for Sips isotherm; and Table 6 shows
the adjustable parameters of Sips model obtained from non-linear
regression of our adsorption data.
4. Conclusions
the calcium salts on the surface of the activated carbons prepared
by impregnation using a calcium solution extracted from egg shell
wastes prior carbonization seemed to play a primary role. Reten-
tion capacities obtained were comparable to those reported for
activated carbons prepared by following conventional activation
routes. Accordingly, the activation process using a calcium solution
extracted from egg shell wastes could be considered as an alterna-
tive and low-cost approach to improve the adsorption properties
of activated carbons for wastewater treatment. Finally, modeling
of the adsorption data pointed out the ability of the Sips model to
fit adequately the experimental results obtained, in comparison to
Langmuir and Freundlich models.

Activated carbons for wastewater treatment could be effectively Acknowledgements

prepared from both jacaranda fruit and plum kernels by the two
simple methodologies considered in this study. In general, results
showed that activated carbons obtained from plum kernels offered
the best adsorption properties for the removal of these priority
water pollutants. Removal of Pb2+ ions by the activated carbons
prepared seemed to be controlled by the textural properties of the
adsorbents. Hence, adsorbents with higher total pore and micro-
pore volumes performed better. The adsorption of AB25 and MB
dyes, however, was strongly conditioned by the surface chemistry
of the adsorbents. For these particular pollutants, the presence of
Authors acknowledge the financial support provided by CONA-
CYT, DGEST, Gobierno del Estado de Aguascalientes, Gobierno
del Municipio de Aguascalientes, Instituto Tecnológico de Aguas-
calientes (México) and Instituto Nacional del Carbón (España).
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