J. Anal. Appl.

Pyrolysis 78 (2007) 185–193

www.elsevier.com/locate/jaap

Characterization of adsorbent materials prepared from avocado

kernel seeds: Natural, activated and carbonized forms
Marı́a P. Elizalde-González a,*, J. Mattusch b,
Alejandra A. Peláez-Cid a, R. Wennrich b
a
Centro de Quı́mica, Instituto de Ciencias, Universidad Autónoma de Puebla, Apdo,
Postal J-55, Puebla, 72571 Pue, Mexico
b
UFZ, Centre for Environmental Research Leipzig-Halle, Department of Analytical Chemistry,
Permoserstr. 15, 04318 Leipzig, Germany
Received 9 December 2005; accepted 28 June 2006
Available online 9 August 2006

Abstract
The development, characterization and application of adsorbents prepared from avocado kernel seeds are described. The preparation comprises
physical activation at temperatures up to 1000 8C and chemical activation with and without H3PO4, with and without carbonization. The resultant
adsorbents have high oxygen content and the main inorganic components are silicon and potassium. After carbonization the surface retains acidic
groups, mainly phenolic moieties. Characterization by adsorption of methylene blue revealed that the initial sorbent exhibited low surface area.
After carbonization and activation the specific surface increased up to 1500 m2 g1. The adsorption capacity was evaluated against basic blue 41.
The results indicated a mayor adsorption capacity of the non-carbonized adsorbent in comparison with carbonized samples, due to the greater
amount of surface acidic groups. The adsorption of basic violet 16 and basic blue 9 was controlled by the interaction with the acidic groups. For the
dyes acid blue 74 and acid green 25, the magnitude of the specific surface area played a mayor role.
# 2006 Elsevier B.V. All rights reserved.

Keywords: Carbonization; Avocado kernel seed; Natural adsorbent; Adsorption from solution; Basic dyes

1. Introduction
Adsorption has proven to be one of the most effective
physicochemical methods for textile wastewater treatment.
There is a growing interest [1] in preparing substitutes for
activated carbon, the conventional and pricy adsorbent
recommended to remove dyes from coloured effluents. In
the past, the regular activated carbon was prepared [2] from
coal/lignite (42%), wood/coconut (45%) or animal bones and
was designated as mineral carbon, vegetal carbon and bone
char, respectively. At present, two low cost adsorbent groups
are under development: (a) naturasorbents obtained from agro-
wastes and naturally occurring materials and (b) carbonaceous
adsorbents obtained by carbonization of naturasorbents.
In the second group the choice is very broad and varies from
wood bark of different trees to fruits, plants and cereals waste.
* Corresponding author. Fax: +52 222 2295525.
E-mail address: melizald@siu.buap.mx (M.P. Elizalde-González).
The encyclopaedic edition of Gupta and Ali [3] compiles the
alternative materials subjected to carbonization for environ-
mental applications and particularly, in dye removal like:
almond shells, olive stones and rice husk. Other innovative
natural materials used in the production of carbonaceous solids
and tested in dye adsorption include, bagasse [4], bamboo [5],
Cassava peel [6], cobs [7], cotton stalks [8], palm seeds [9],
peanut hulls [2,5], plum kernels [10,11], rice husk [12], sawdust
[12,13], and straw [5]. Naturasorbents have been mainly
obtained from plant wastes like maize, coconut and sugar cane,
and fruits peel like orange and banana. The adsorption
properties of seeds, stones and pits have been reported only
for carbonized samples. Although there is not clear evidence
that the non-carbonized forms exhibit low efficiency, recent
research suggests that carbonization yielding high specific
surface area magnitudes is the only way of preparing effective
adsorbents from naturally occurring materials.
Fruit seeds have not received serious consideration as
sorbents. However, there are considerably high amounts of
waste arising from human consumption or food-processing

0165-2370/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2006.06.008
186 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193

Table 1
Prepared adsorbents, magnitude of the relative specific surface area Ssp and organic elemental analysis
Adsorbent code Sample description Ssp (m2 g1) Ash content (%) Elemental analysis
C (%)  S.D. H (%)  S.D. N (%)  S.D. O (%)
AGAP Natural, without activation 53 (a) 2.2 44.6  0.1 6.3  0.1 0.7  0.1 48.4
and carbonization
AGAP1 Activated with peroxide 29 (a) 0.3 45.5  0.2 6.3  0.1 0.9  0.1 47.3
AGAP-800 Carbonized at 800 8C 227 (b) 9.5 78.9  0.1 1.5  0.1 1.1  0.1 18.5
AGAP-1000 Carbonized at 1000 8C 452 (b) 15.4 75.0  1.2 1.2  0.1 0.9  0.1 22.9
AGAP-P-800 Activated with H3PO4 and 1802 (b) 12.5 76.4  0.3 1.7  0.1 1.0  0.1 20.9
carbonized at 800 8C
AGAP-P-N-800 Activated with H3PO4 and 1590 (b) 5.3 73.1  0.2 1.9  0.1 1.1  0.1 23.9
carbonized under nitrogen
flow at 800 8C
Determined by adsorption isotherms of (a) methylene blue from aqueous solutions at 298 K and (b) nitrogen at 196 8C using Langmuir equation.

plants. In the case of the studied avocado, 10–13% of the fruit
weight corresponds to the kernel seed, and it is garbage after
consumption. The avocado seeds constituents are reported to be
mainly phenolic [14] and proanthocyanin compounds [15].
Regarding the utilization of fruit seeds as sorbents, their
properties have to be studied by chemical analysis and surface
characterization. This information is valuable for the final
adsorbent produced by activation and carbonization processes,
as well as for its adsorption properties.
In this study, the relevant chemical parameters and the
surface characteristics of the AGAP sorbents prepared from
avocado kernel seeds were analyzed. The adsorption of basic
blue 41 from aqueous solutions by the natural sorbent was
investigated and was compared with the capacity of activated
and carbonized samples. By natural form of the sorbent we
mean washed and dried particles obtained from avocado kernel
seed. The activated forms are defined in this study as follows:
natural samples chemically activated by washing with peroxide
or by impregnating with H3PO4. Summarizing, this work
handles one sample in its natural form (AGAP), one sample
chemically activated (AGAP1), two samples with physical
activation (AGAP-800 and AGAP-1000), and two samples with
chemical and physical activation (AGAP-P-800 and AGAP-P-
N-800). Four carbonized samples denote natural or chemically
activated forms after thermal treatment.
2. Experimental
2.1. Materials
The adsorbent material designated as AGAP, its activated
(AGAP1) and carbonized forms were obtained from avocado
kernel seeds purchased in local markets. The seeds were
washed with distilled water, dried at 50 8C for 24 h, cut and
sieved to obtain the desired size fractions (1–2 mm). Dry
particles of AGAP were treated with H2O2 (30% (v/v), Baker)
under continuous stirring for 3 h to produce AGAP1. Washing
with distilled water was accomplished until a skimmed
decantation effluent was obtained. Carbonization was carried
out in a horizontal tubular quartz reactor provided with gas inlet
and outlet located in a temperature/time programmed furnace
(5 8C). The heating rate was 5 8C min1. Isothermal time at
maximum heat treatment temperature was 4 h. After that, the
system was cooled down to room temperature in atmosphere of
the carbonization products or in N2 atmosphere (inlet flow
2 l min1) at a cooling rate of 15 8C min1. Natural AGAP
samples were impregnated with H3PO4 by adding 250 mg of
the sorbent to 1 ml of phosphoric acid (85 v/v, Merck). The
activation procedures are presented in Table 1. The avocado
(Persea americana) waste kernels stemmed from Hass
cultivars. The following dyes were used: basic blue 41
(BB41), basic violet 16 (BV16), and acid green 25 (AG25)
from Clariant; basic blue 9 (BB9) from Sigma, acid blue 74
(AB74) from Hartman Leddon Co., and reactive black 5
(RBK5) from Ciba. Methanol, acetonitrile HPLC grade
(Burdick & Jackson) and deionised water were used in the
chromatographic analysis.
2.2. Methods
Organic elemental analysis was performed with a CHN 1000
Leco elemental analyzer calibrated with standard orchard
leaves (U.S. NBS). The oxygen content was obtained indirectly
by difference. Elemental analysis results are expressed on a dry
basis. Ash content of AGAP and AGAP1 was determined at
550 8C (2 h) and at 650 8C (4 h) for the carbonized materials.
Loss on ignition (LOI) was calculated as the weight loss,
expressed as a percent of the original weight after burning off
1 h at 1050 8C in a platinum crucible under atmospheric
conditions. The inorganic chemical composition was deter-
mined by X-ray fluorescence spectrometric analysis with a
sequential X-ray spectrometer (Siemens SRS 3000). Quanti-
fication of the functional groups was performed according to
the Boehm’s titration methodology [16] for activated carbons
by using analytical grade reagents. Nitrogen adsorption
isotherms were measured at 196 8C (Sorptomatic 1900
surface analyzer) for specific surface area and pore volume
determinations. The pore size was calculated by the Barret–
Joyner–Halenda equation. Micrographies were taken with an
Olympus SZX-12 equipment. A Nicolet Magna FT-IR-750
spectroscopy apparatus was employed to determine the
presence of functional groups. The TG-FT-IR consisted of a
 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193
Fig. 1. Optical microscopy (25) of the surface of AGAP (a) and AGAP1 (d) before carbonization and of the carbonized AGAP samples: AGAP-800 (b), AGAP-
1000 (c), AGAP-P-800 (e) and AGAP-P-N-800 (f).
TG 209 Netzsch and a Vector 22 from Bruker Optik GmbH
spectrometer with a gas cell (230 8C), connected by a heated
(200 8C) transfer line. Samples were heated in a stream of
nitrogen (15 ml min1), or of O2/N2 (5/95) at 25 ml min1 with
a rate of 10 8C min1 up to 990 8C. The IR spectra were
recorded with a resolution of 8 cm1 in the range 4000–
600 cm1. Specific gas profiles were extracted from the TGA
curves at the corresponding spectroscopic ‘‘windows’’ indi-
cated in parenthesis: carbon dioxide (2380–2320 cm1), carbon
monoxide (2180–2140 cm1), and water (1560–1500 cm1).
Thermogravimetric and spectroscopic files extraction was
performed with the software Proteus (Netzsch) and OPUS
(Bruker), respectively. Multifiles treatment was accomplished
with the GRAMS/32 software. Combustion efficiency was
calculated by integration of the respective areas A under the
thermogravimetric curves as 100ACO2 =ðACO2 þ ACO Þ.
To study the dyestuffs adsorption, BB41 was chosen.
Dyestuffs used to test adsorbents’ efficiency were: BV16,
AG25, BB9, AB74 and RBK5. Dyes solutions were prepared
without pH adjustment in deionised water (Milli-Q reagent
grade water). The respective pH and pKa values were: BB41 4.2
and 8.7, BV16 3.8 and 9.2, BB9 5.0 and 9.4, AB74 5.5 and 10.5,
RB5 5.6 and 9.5, AG25 pH 5.6 [1]. Methylene blue (BB9) was
used in the determination of the specific surface of the non-
carbonized samples AGAP and AGAP1, which cannot be
subjected to evacuation, heating at temperatures above 60 8C,
and cooling at temperatures below 0 8C required for a nitrogen
adsorption measurement. Adsorption isotherms were measured
at room temperature (25 8C) in batch experiments by using
polycarbonate cylindrical cells with a lid, definite amounts of
adsorbent and a fixed volume of the aqueous dye solutions (0.5–
3.0 mM). After stirring for 1 h, the dye solution was left in a
temperature-conditioned room. The solution that resulted from
the adsorption equilibrium after 24 h was separated from the
exhausted adsorbent and analyzed by high performance liquid
chromatography (HPLC). Mobile phase composition was
methanol–buffer. A cross section molecular area value of 98
and 16.4 Å2 was taken for methylene blue and nitrogen,
respectively, according to [17].
187
3. Results and discussion
3.1. Adsorbents characterization
3.1.1. Morphology, specific surface area and composition
The morphology of particles (1–2 mm) of the adsorbent
AGAP in its natural, activated, and carbonized forms is
depicted in Fig. 1. A dense structure and quite compact can be
observed in both natural and carbonized materials. Table 1
summarizes the specific surface area of each sample. For
uniformity, values were calculated by the Langmuir equation
considering monolayer formation in the methylene blue
concentration range 0.5 < Cinitial < 3.0 mM for the non-
carbonized samples and until the nitrogen relative pressure p/
p0 = 0.3 for the carbonized ones. The magnitude of the
specific surface increased with carbonization and reached a
magnitude >450 m2 g1 for the sample treated at 1000 8C
(AGAP-1000) and >1800 m2 g1 for the sample chemically
activated with H3PO4 at 800 8C (AGAP-P-800). Waste
Cassava peel, [6] yielded a more efficient carbon upon dyes
and heavy metals when the cellulosic material was activated
with phosphoric acid (490 m2 g1) than with thermal
treatment (270 m2 g1) due complementary to the presence
of phosphate groups. For AGAP, the specific surface area
was enhanced 100% when the carbonization temperature
increased 200 8C.
The elemental composition of the resulting sorbents is
presented in Table 1. The relevant information is the high
oxygen content (>45%) of the raw and activated material, its
diminution and preservation in a considerable extent (>20%)
in the carbonized products. According to current knowledge,
carbonization at high temperature (>600 8C) yields materials
with a low amount of oxygen surface groups and basic
character [18,19]. Furthermore, the nitrogen content in all the
samples is higher than that in wood and cherry stones, for
example [20]. From the loss on ignition (LOI) values given in
Table 2, which represent the percentage weight lost on ignition
and gives a crude measure of the organic content of the sample
it can be seen that the volatile organic matter content in the
188 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193

Table 2
Loss on ignition values (LOI), normalized inorganic elemental composition, and absolute phosphorus, iron and zinc content of the prepared adsorbents
Adsorbent LOI Relative inorganic composition (%) Absolute content
Na2O MgO Al2O3 SiO2 K2O CaO TiO2 MnO P2O5 Fe2O3 Zn
(%) (mg kg1) (mg kg1)
AGAP 97.2 2.1 7.9 2.4 38.4 44.8 3.1 1.1 0.3 0.3 50 30
AGAP1 98.9 3.2 10.2 5.7 69.0 1.6 7.6 2.1 0.5 0.1 50 20
AGAP-1000 88.4 1.6 10.1 2.5 14.1 67.3 3.6 0.5 0.2 4.1
AGAP-P-N-800 87.6 3.5 12.0 0.7 72.4 2.1 5.9 2.7 0.6 11.0

prepared adsorbents is very high. Then, the inorganic elements
in the raw material are minor but important, since they
concentrate progressively in the final carbonized sample.
Moreover, silica and potassium are the main inorganic
constituents of the avocado seed (see Table 2). The mineral
components could be most likely in the form of silicates or
oxides, which can be correlated with the high oxygen content.
In general, the chemical activation procedure leached the
potassium in the sample AGAP1 (prepared with peroxide) and
in AGAP-P-N-800 (obtained with H3PO4 and physical
activation at 800 8C in N2), while the physical activation at
1000 8C lowered the SiO2 content. The high phosphorus
content in the chemically activated sample AGAP-P-N-800
demonstrates the retention of phosphorous species despite
exhaustive washing.
Fig. 2. FT-IR spectra of the prepared adsorbents in KBr pellets: AGAP (a),
AGAP-800 (b), AGAP-1000 (c), AGAP-P-800 (d) and AGAP-P-N-800 (e).
3.1.2. Bulk and surface functional groups
The normalized infrared spectra of the samples are shown in
Fig. 2. In the region 4000–3000 cm1 it appears a strong band
with different intensity, which is broader (3740–3000 cm1) in
the raw AGAP sample, than in the activated and carbonized
materials (3670–3000 cm1). The nNH and nOH bands are not
separated and the position (3410 cm1) reveals that the N–H
group is present in all the samples. Hydroxyl groups may come
from the anthocyanins [15], while the amino groups may
represent in the seed aminoacids as it was found here in the
elemental analysis (see nitrogen content in Table 1). Bands
corresponding to other functional groups are different in the
natural AGAP adsorbent and in their carbonized forms. For
example, the band at 2920 cm1 corresponding to C–H
stretching in aliphatic structures, disappeared in the two
carbonized samples subjected to physical activation (800 and
1000 8C) (Fig. 2b and c) and in the two samples chemically
activated with H3PO4 (Fig. 2d and e). The minor lactone band at
1740 cm1 (Fig. 2a) cannot be observed after carbonization of
the samples. The spectrum of AGAP exhibits a band with
maximum at 1640 cm1, which can be assigned to primary
amide (overlapped with NH vibration) or to the C C stretching
vibration in polynuclear aromatic compounds and probably
corresponds to the flavonol antioxidants and anthocyanins
present in the sample. The band at 1460–1330 cm1 (OH
vibration) is typical for celluloses and appears as shoulder in the
carbonized samples AGAP-800 and AGAP-1000. In the
samples activated with H3PO4, AGAP-P-800 and AGAP-P-
N-800 this band comes together with the band at 1560 cm1
indicating the presence of C C bonds. The region between
1300 and 900 cm1 presents marked differences in the
carbonized samples with respect to the raw AGAP. Clear
bands at 1160, 1100 and 1020 cm1 assigned to C–O stretching
denote tertiary, secondary and primary hydroxyl groups in
AGAP (Fig. 2a). As a result of carbonization with physical and
chemical activation, these three well defined bands became a
broad band (1300–900 cm1) (Fig. 2b–e) indicating the loss of
primary hydroxyl groups and the formation of ethers. Since the
use of phosphoric acid is common in the chemical activation of
naturasorbents, bands appearing at 1190 and 1070 cm1 have
been attributed to phosphorus oxides from thermal decom-
position of H3PO4 [2,6,8,21,22], respectively, to P–O–P
symmetric and P–O–C asymmetric stretching vibrations
[23]. However, spectra of the samples carbonized without
H3PO4 impregnation (spectra b and c) exhibited a broad band
(1300–900 cm1) in this region with a noticeable band at
 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193 189

Table 3
Functional groups on the surface of the carbonized naturasorbent AGAP
Adsorbent Basic groups Acidic groups (mmol m2) Total groups (mmol m2)
(mmol m2)
Carboxylic Lactonic Phenolic Total
AGAP 0 0 5.7 18.9 24.5 24.5
AGAP1 0 0 13.8 24.1 37.9 37.9
AGAP-800 9.1 0 0.3 4.4 4.7 13.8
AGAP-1000 0 0.6 1.8 3.9 6.3 6.3
AGAP-P-800 0 0.1 2.3 0.5 2.9 2.9
AGAP-P-N-800 0 1.6 0 1.0 2.6 2.6

1070 cm1. Impregnation with phosphoric acid produced bands 300 and finished at 760 8C. The peak at about 290–315 8C in
(spectra d and e) corresponding to phosphine oxides R3P O natural avocado seed (Fig. 3A left) and in its activated form
(P O aromatic at 1190 cm1), and phosphates P–O–C (P–O (Fig. 3B left), was also observed in cotton stalks [8] and probably
aliphatic at 1020 cm1). Only in the sample impregnated and corresponds to hemicelluloses [27]. The second peak of the
carbonized under under nitrogen stream (spectrum e), a activated sample is broad and shifted indicating the presence of
shoulder corresponding to phosphorous esters R2PO–O-Aryl different moieties, which oxidize at higher temperatures
(P–O at 900 cm1 accompanied by the band at 1160 cm1), (540 8C). The comparison of the peaks in Fig. 3A and C shows
was perceptible. The vibration of Si(Al)O4 tetrahedra (band at that the sample carbonized at 800 8C also carries groups
555 cm1) is evident in all carbonized samples. decomposing at about 450 as the natural avocado seed AGAP.
It follows that the bulk chemical composition of AGAP and These groups can be different in so far as the profiles are not
its carbonized forms consists of different chemical functional identical, or may contain partially the same groups, which
groups. Band intensities revealed that the most abundant are:
hydroxyl, aromatic and phenolic in the natural AGAP, and
hydroxyl, carboxyl, and ether in the carbonized samples. Data
of the surface functional groups obtained by Boehm’s titration
are shown in Table 3. Both the native AGAP and the activated
AGAP1 adsorbents exhibit a greater amount of surface
functional groups than the carbonized forms. The most
interesting results are the absence of basic groups (with
exception of the avocado seed sample carbonized at 800 8C)
and the abundance of phenolic groups. This result can be
explained from the chemical composition of the avocado seeds
and was already observed in the IR spectra. Carbonization and
chemical activation with H3PO4 led to the development of
surface carboxylic groups and to the diminution of the total
amount of surface groups. It has been reported [24] that the
adsorption capacity of an adsorbent upon a basic dye increased
for carbonaceous materials with low oxygen content, low
acidity and high basicity. Another view [25] was that the
capacity upon basic blue 41 increased with the amount of acid
groups on the surface of naturasorbents obtained from maize.
Here, as it will be discussed later, the adsorbents obtained from
avocado seeds allow the comparison of the adsorption capacity
between natural and carbonized samples carrying only acidic
groups.
The evolution curves of carbon monoxide, carbon dioxide and
water recorded in synthetic air during TG-FT-IR analysis are
presented in Fig. 3. In this atmosphere the formation of CO and
CO2 followed the same pattern in natural, activated and
carbonized samples. With the non-carbonized samples one
can register two effects in context with the weight loss, while with
carbonized adsorbents only one effect is ascertainable. Two
Fig. 3. Evolution profiles of carbon monoxide and carbon dioxide (left side),
exothermic peaks at 550 and 630 8C indicating two types of and of water (right side) in synthetic air stream of the samples AGAP (A),
carbonaceous material were also observed in a cellulose-pitch AGAP1 (B), AGAP-800 (C), AGAP-1000 (D), AGAP-P-800 (E) and AGAP-P-
composite [26]. In AGAP the release of volatile matter started at N-800 (F). Y-axis in normalized scale.
190 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193
appear overlapped in the carbonized sample. The curve of the
sample carbonized at 1000 8C (Fig. 3D) is similar to that of the
activated sample AGAP1 (Fig. 3B). Both curves present a flat
maximum at 540 8C and for AGAP-1000 an additional spike at
563 8C appeared. After activation with H3PO4, the profiles
(Fig. 3E and F) of the carbonized samples are very similar and
shifted to higher temperatures typical for secondary carboniza-
tion products.
The water evolution profiles (right side of Fig. 3) appearing at
temperature <200 8C can be assigned to moisture. Evolution
profiles at temperatures higher than 300 8C can be correlated
with the decomposition of the material, under production of CO
(or CO2) + H2O since they appeared at the same temperatures as
the CO and CO2 profiles maxima, i.e., at 300, 453, and 541 8C.
The samples impregnated with H3PO4, did not show the high
temperature water peak, suggesting the known dehydration effect
of H3PO4 [23]. In order to study the thermal decomposition and
not the oxidation of the carbonized samples, the CO (Fig. 4A) and
CO2 (Fig. 4B) evolution in nitrogen atmosphere was measured.
The TG-FT-IR tracings showed various effects above 400 8C.
Only the samples with chemical and physical activation
exhibited a peak-shaped release of CO2 at 880 8C (Fig. 4B).
A plateau-shaped effect between 500 and 850 8C was observed
for the other materials. Except for AGAP-P-N-800, carbon
monoxide evolved in a minor extent than CO2 (Fig. 4A). In the
natural avocado seed, and in the samples without H3PO4
impregnation, CO evolved at higher temperatures. This is related
with the combustion efficiency of a material, which oscilated
between 10 and 14% for the samples AGAP, AGAP-800 and
AGAP-1000 and turned 24% in AGAP-P-800 and 57% in
Fig. 4. Evolution profiles of carbon monoxide (A) and carbon dioxide (B) in
inert atmosphere (N2) of the carbonized samples of the adsorbent AGAP.
AGAP-P-N-800. According to [24], pyrone and carbonyl
moieties are formed in this temperature range. The last groups
could be observed by IR spectroscopy in the carbonized avocado
seed samples as shown in Fig. 2. Other authors [23] assign mass
loss at 750–920 8C to volatilization of phosphorus compounds.
However, cotton stalk adsorbents impregnated with phosphoric
acid [8] presented a single peak at 607 8C and the adsorbent
AGAP-1000 obtained without H3PO4 impregnation presented an
additional mass loss at 900 8C. Hence, statements about the
decomposition of assigned groups in this temperature range must
be regarded with caution. Additionally, it was also demonstrated,
that inorganic components [26] had influence on the appearance
of two TG peaks.
3.1.3. Texture
Textural characterization of the following carbonaceous
materials prepared from naturasorbents has been reported:
cotton stalks [8], plum kernels [10], corncob [7], bagasse [4],
peanut hulls [2], coffee bean husk [21], nutshells [28], and
peach and olive stones [22]. Fig. 5 shows the nitrogen
adsorption isotherms measured at 196 8C, corresponding to
the carbonized avocado seeds samples. The isotherm of the
avocado adsorbent prepared at 800 8C is characteristic for
materials with wide micropores with relatively uniform pore
sizes. The lack of adsorption hysteresis indicates the absence
of mesoporosity, whereas in the sample carbonized at 1000 8C,
Fig. 5. Adsorption (full symbols) and desorption (open symbols) isotherms of
nitrogen at 196 8C on the carbonized AGAP samples.
 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193 191

Table 4
Textural properties of the carbonized samples prepared from avocado naturasorbent AGAP
Sample SBET (m2 g1)a SDR (m2 g1)b Vp (cm3 g1) % of micropore volume Average pore diameter (Å) Yield (%)
AGAP-800 143 220 0.073 93 14.3 20
AGAP-1000 283 437 0.147 95 14.3 8
AGAP-P-800 1069 1558 1.053 53 14.5 9
AGAP-P-N-800 960 1392 1.023 48 14.4 18
a
SBET, specific surface calculated by using Brunauer–Emmett–Teller equation.
b
SDR, specific surface calculated by using Dubinin–Radushkevich equation.

mesoporosity begins to develop as seen from the obtuse

adsorption–desorption loop. Carbonization at 800 8C with
chemical activation (H3PO4 impregnation) produced hetero-
geneity of the micropore size and mesoporosity. The type H4
hyteresis loop is evident in the samples AGAP-P-800 and
AGAP-P-N-800 and indicates the formation of slit-shaped
mesopores, whereby activation under nitrogen stream did not
influence pore evolution, as it can be seen from the analogous
adsorption isotherms. Similar changes of the isotherms
shapes by chemical activation have been observed for peach
and olive stones and coffee beans, and were not found for the
physical activation of corncob [7]. The surface and pore
structure parameters derived from these isotherms are
compiled in Table 4. As it can be seen, compared with
the adsorbents with thermal activation (AGAP-800 and
AGAP-1000), the chemical activation with H3PO4 led to a
significant increase in specific surface area considering both
multilayer adsorption (BET equation) and microporosity (DR
equation), whereas the sample activated under nitrogen
AGAP-P-N-800 partially decreased its surface area. Both
specific surface area and micropore volume of the sample
carbonized at 1000 8C are practically twice as large as with the
sample carbonized at 800 8C. It is known, that the alkaline
elements, in particular potassium [29], show a catalytic effect
on the gasification of carbonaceous materials, thus affecting
positively the magnitude of the specific surface area as it has
been reported in [30]. Similar high surface magnitudes have
been reported for physically activated corncob waste, bagasse,
and chemically activated cotton stalks, coffee beans, peach and
olive stones.
With the exception of the materials prepared from plum
kernels [10] and corncob [7], the carbonaceous sorbents, which
have been subjected to characterization in the literature, have
not been tested in dye adsorption.

3.2. Adsorption of basic blue 41

The characterization of non-carbonized natural adsorbents

in terms of acidic and basic groups is seldom reported [25],
although this aspect plays an important role in dye adsorption.
From the adsorption isotherms on the avocado seed kernel
AGAP and on activated AGAP1 shown in Fig. 6A it can be
observed that saturation of the adsorbent was not reached for Fig. 6. Adsorption isotherms of basic blue 41 on non-carbonized (A) AGAP and
activated AGAP1, and on carbonized samples (B and C): AGAP-800, AGAP-
the studied concentrations range. The not activated AGAP 1000, AGAP-P-800, and AGAP-P-N-800. Temperature 24 8C, adsorbent dosage
(53 m2 g1) presented a lower adsorption capacity upon basic 0.01 mg ml1. Dotted line: adsorption with adsorbent dosage 0.02 mg ml1 on
blue 41 (see formula in Table 5) in comparison with AGAP1 AGAP-800. Star symbols: points calculated by Langmuir equation.
192 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193
Table 5
Maximum adsorption capacity of the studied adsorbents against basic blue 41 due to monolayer formation calculated according Langmuir adsorption isotherm
equation
Adsorbent Specific and surface saturation capacity
1
am (mg g ) am (mmol m )
AGAP 72.6 3.22
AGAP1 43.4 3.21
AGAP-800 67.1 1.04
AGAP-1000 130.2 1.02
AGAP-P-800 125.3 0.26
AGAP-P-N-800 86.6 0.20
(29 m2 g1). Since adsorption magnitudes and thus adsorption
capacities are expressed in mmol m2, this result is due to the
amount of surface functional groups in both adsorbents (see
Table 3) and not to the magnitude of the specific surface area.
Let us examine the adsorption of BB41 on the carbonized
adsorbents obtained from the non-activated AGAP. From the
curves shown in Fig. 6B, monolayer formation leading to
adsorbent saturation could be established. It was found that
adsorption capacity of the avocado seeds carbonized at 800
and 1000 8C upon BB41 was lower than that on the not
carbonized adsorbents (see scale in Fig. 6A). Furthermore, the
capacity of AGAP-1000 (Ssp = 440 m2 g1) was similar than
that of AGAP-800 (Ssp = 220 m2 g1), due to the larger
amount of total functional groups on the surface of AGAP-800
(see Table 3). The adsorption isotherms depicted in Fig. 6C
illustrate that the adsorption capacity of the high-surface
adsorbents, AGAP-P-800 (Ssp = 1070 m2 g1) and AGAP-P-
N-800 (Ssp = 960 m2 g1), upon BB41 was even smaller than
that of the thermally activated avocado adsorbents AGAP-800
and AGAP-1000. The evidence for low capacity in solids with
high surface area, but low amount of functional groups is
conclusive. The calculated saturation capacities according to
Langmuir monolayer adsorption model are presented in
Table 5. An important point in comparing different solids
against one adsorbate is the construction of absolute
adsorption isotherms, i.e., determining adsorption magnitudes
as surface capacities per surface unity am (in mg m2 or
mol m2). From the am values presented in the third column in
Table 5 and the number of total groups (last column in Table 3)
the mentioned correlation can be established; whereas it is not
clear on the basis of the capacity am in mg g1 (second column
in Table 5).
3.3. Removal of basic and acid dyes
As shown from the bars height in Fig. 7, the removal
efficiency of non-carbonized (AGAP), thermally activated by
carbonization at 800 8C (AGAP-800) and carbonized at 800 8C
in N2 stream after chemical activation with H3PO4 (AGAP-P-
N-800) against two additional basic dyes, different from BB41,
Formula of basic blue 41
2
S.D. R
0.01 0.98288
0.02 0.98091
0.01 0.99973
0.01 0.99830
0.01 0.99619
0.03 0.99215
under similar pH conditions was not controlled necessarily by
the magnitude of the surface area. Removal efficiency was
similar (>90%) for the basic dye basic violet 16 on AGAP and
AGAP-P-N-800, whereas on AGAP-800 it was about 60%.
Also for the basic dye basic blue 9, the removal efficiency was
higher by the adsorbent AGAP with 53 m2 g1 than the
efficiency (40%) of AGAP-800 exhibiting 227 m2 g1, due to
the higher amount of acidic groups. It is also possible that the
basic groups present in AGAP-800 influenced this result. The
low efficiency of AGAP against the dyes acid blue 74 and acid
green 25 can be explained by the repulsive interaction with the
acidic groups on the surface. For these two acidic dyes, the
large magnitude of the specific surface area of AGAP-P-N-800
determined removal efficiency. The lowest removal efficiency
of the three avocado seed sorbents was observed upon the
reactive dye RB5, in comparison with the basic and acid dyes.
Nevertheless, the difference between the efficiency of the
non-carbonized AGAP (25%) and AGAP-P-N-800 (39%)
avocado adsorbents is not proportional to their differentiation
in the specific surface area magnitude (53 m2 g1 versus
1590 m2 g1). This example suggests that during adsorption of
Fig. 7. Comparison of the removal efficiency at 24 8C of non-carbonized
AGAP and carbonized AGAP under two different conditions, against basic
(BB41, BV16 and BB9), acid (AB74 and AG25), and reactive (RBK5) dyes
from 400 mg l1 solutions using adsorbent dosage 0.01 mg ml1.
 M.P. Elizalde-González et al. / J. Anal. Appl. Pyrolysis 78 (2007) 185–193
reactive dyes from solution, additionally to physical, also a
chemical interaction takes place.
Apart from the adsorption efficiency noted in the bars, when
observing the am values in Table 5, the results demonstrated
certain superiority of the avocado carbonized sorbents in
comparison, e.g., with activated carbon prepared from sawdust
[13] tested for direct blue 2B (am < 1 mg m2), rice husk [12]
used for adsorption of acid yellow 36 (am < 0.3 mg m2),
corncob [7] (am = 0.8 mg m2) and plum kernels [11]
(am < 0.6 mg m2), both employed in the removal of basic
red 22.
4. Summary
A series of environmentally friendly adsorbents for dye
removal has been obtained by simple activation of avocado
kernel seeds waste. The adsorption capacity of these natur-
asorbents was tested upon basic blue 41. The sorbents of the
series AGAP are superior than activated carbon prepared from
corncob and plum kernels, since they adsorb higher amounts of a
dye of the basic class. Complete analysis and characterization
allowed assessment of the most important features of the
prepared adsorbents. The adsorbents have high oxygen content
and the main inorganic components are silicon and potassium.
Before and after carbonization the surface supports acidic
groups, mainly phenolic moieties. Carbonization created
microporous solids and with a temperature increment of
200 8C specific surface area was doubled. Chemical activation
with H3PO4 and carbonization at 800 8C created mesoporous
adsorbents with specific surface area up to 1500 m2 g1, whereas
chemical activation and carbonization under nitrogen stream did
not affect substantially specific surface area and microporosity.
The results indicated a mayor adsorption capacity of the non-
carbonized adsorbent upon basic dyes in comparison with
carbonized samples, due to the higher amount of surface acidic
groups, while acid dyes were better removed by samples
exhibiting large specific surface area owing to the repulsion
with the acidic surface groups on non-carbonized samples.
Acknowledgements
This research was supported by CONACyT (project SEP-
2004-C01-46377). AAPC thanks CONACyT for a scholarship
grant (130497). Mobility financial support was provided by
BMBF-DLR (Germany, project MEX-01/008), and CONACyT
193
(Mexico, 46377-2004). We thank Dr. W. Geyer (UFZ,
Germany) for his contributions.
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