Colloids and Surfaces A: Physicochem. Eng.

Aspects 254 (2005) 107114

Adsorption interaction between natural adsorbents and

textile dyes in aqueous solution
M.M. Davila-Jimeneza , M.P. Elizalde-Gonzalezb, , A.A. Pelaez-Cidb
b

a Facultad de Ciencias Qumicas, Universidad Aut

onoma de Puebla, Apdo. Postal J-55, Puebla 72571, Pue, Mexico
Centro de Qumica, Instituto de Ciencias, Universidad Autonoma de Puebla, Apdo. Postal J-55, Puebla 72571, Pue, Mexico

Received 27 April 2004; accepted 17 November 2004

Available online 4 January 2005

Abstract
Agricultural wastes from maize culture fields were prepared and activated yielding the natural absorbents designated as SOMAP, SOMAP1,
SOMAP2, HELAP, HELAP1, SAGAP, and SAGAP1. The samples were further characterized using microscopy, FTIR spectroscopy, titration,
and adsorption from solution. The dry and wet methods of analysis confirmed the presence of functional groups (hydroxyl, carboxylic,
phenolic, and lactonic) in the bulk and on the surface, respectively. Each prepared solid sample was tested for adsorption ability using aqueous
dye solutions of basic blue 41 (BB41), acid blue 74 (AB74), and reactive black 5 (RB5). The adsorption affinity decreased according to
BB41 > AB74 > RB5. For BB41 the relative adsorbent saturation followed the series: SOMAP2 < SOMAP1 < SOMAP, HELAP < HELAP1
and SAGAP < SAGAP1. Adsorption equilibrium concentrations were followed by HPLC with diode array detection. The equilibrium data
fitted well with both Langmuir and Freundlich models of adsorption. The values of the Freundlich exponent 1/n correlated with the variance
of the group distribution curves. The monolayer capacity of all studied adsorbents using the basic dye BB41 correlated acceptably with the
corresponding amount of total acid groups on the adsorbent surface.
2004 Elsevier B.V. All rights reserved.
Keywords: Natural adsorbents; Surface chemistry; Adsorption; Dyes

1. Introduction
Investigations have evaluated inexpensive alternative materials [1,2] as potential adsorbents for pollutants and
coloured compounds. The options considered in dye removal
using adsorption [3,4] included inorganic synthetics [5] and
natural materials [2], however, the use of natural organic
solids has grown exponentially. Among organic compounds,
many materials fill the potentiality demand for dye removal,
without being economical. Naturally occurring materials and
wastes [611] improve the collection of low cost adsorbents,
while being environmental acceptable. A number of articles
have been published on the use of maize cobs [12], palm-fruit
bunch particles [1315], eucalyptus bark [16], cotton [17],

Corresponding author. Tel.: +52 222 229 5500; fax: +52 222 229 5525.
E-mail address: melizald@siu.buap.mx (M.P. Elizalde-Gonzalez).

0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.11.022

sunflower stalks [18], and wheat straw [10] as adsorbents for

dye removal. The examination of the textile dye removal using novel adsorbents is usually conducted by evaluating their
performance against activated carbon. Carbon is neither economical nor very efficient due to its non-polar nature in its
not activated form and due to the polar nature, in most cases,
of the dyes. Therefore, activation is often used to introduce
polar groups for different applications of the carbonaceous
adsorbents. Carbonisation [1924] of natural materials and
wastes (cob, coir pith, rice husk, sawdust, and plum kernels)
also occupy a position in the production of inexpensive adsorbents. Reports on natural adsorbents in studies involving acid
[1,2,9,12,17,21,22], basic [1,2,6,1115,18,21], disperse [2],
direct [18] and reactive [7,10,16] dyes investigated the feasibility of their use for the removal of dyestuffs from model
aqueous solutions [5,6,8,9,1115,18]. Some scientists have
studied synthetic dye wastewater [2,7,10,16] claiming that

108

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

they investigated wastewater [18] and reported in some cases

molecules [8,11,18,22,26], which are not typical textile dyes.
Like other substrates, the adsorption of dyes is mainly
dependent on the dyes properties and structure, and to an
equal extent on the surface chemistry of the adsorbent. When
carbon adsorption is applied, the texture and surface functional groups of the carbon sample are unfortunately neither
explored nor highlighted. Investigations describing the adsorption of dyes on non carbonaceous solids rarely explain
[1,2,68,1014,17,18,25] the role of the surface chemistry
and report [1,6,1013] only on the adsorption capacity, and
to some extent on the effect of various parameters influencing
the adsorption process [2,7,8,11,16,18].
The aim of this study was to present the morphology, texture, bulk chemical nature, and surface chemistry of a set
of natural adsorbents using microscopy, adsorption from solution, FTIR spectroscopy, and Boehm titration. This study
provides evidence of the relationship between the surface
chemistry and the functionalities of three different types of
textile dyes in aqueous solutions at low adsorption magnitudes.

2. Experimental
2.1. Materials
The adsorbent materials (see Table 1) were prepared from
agricultural waste of maize collected in Puebla (Mexico), by
washing (SOMAP, HELAP and SAGAP) or by washing and
activation (SOMAP1, SOMAP2, HELAP1 and SAGAP1)
[26,27]. Activators A and B consisted of a chlorinated and
oxygenated agent, respectively [27]. The following dyes were
chosen because of their extended regional use in the textile industry: basic blue 41 (BB41), acid blue 74 (AB74),
and reactive black 5 (RB5). Their formulae are presented in
Table 2. They were used as received and the relative content
in the samples determined by HPLC at 220 nm was 7095%.
Other components could correspond to salts, fillers, dyestuff
Table 1
Prepared adsorbents, their raw material, activation and magnitude of the
relative specific surface determined by adsorption isotherms of methylene
blue from aqueous solutions
Raw material

Activation
procedure

OM

none
B

HEL

none

SOMAP

42

SOMAP1

40

SOMAP2

90

HELAP

60

HELAP1

50

HELAP1a

none

Ssp (m2 g1 )

SAG

Adsorbent

SAGAP

50

SAGAP1

30

Ssp determined by nitrogen adsorption at 77 K and the BET equation.

intermediates or compounds, which served as start materials in the dye synthesis. BB41 (C21 H27 O3 N4 SCl) was a
Clariant product (no. 11154) and it is a basic dye of the azo
type. AB74 (C16 H8 O8 N2 Na2 S2 ) was purchased from Hartman Leddon Co. (product no. 242) and is an indigoid acid
dye. RB5 (C26 H21 O19 N5 Na4 S6 ) is produced by Ciba as reactive dye of the azo-sulphonated type. Dyes solutions were
prepared without pH adjustment in the concentration range
from 0.5 to 3 mM in deionised water obtained from a Milli-Q
reagent grade water system. Deionised water was also used
in the chromatographic analysis together with methanol and
acetonitrile HPLC grade (Burdick and Jackson). Methylene
blue used as probe molecule in the determination of the specific surface was a Sigma product. Phosphate buffer and the
reagents used in the Boehms titration were prepared using
reagent grade salts from J.T. Baker. The carbon samples used
for comparison of the surface functional groups were Carbon
Vulcan XC72 GP-3037 and Bone black from Sigma.
2.2. Methods
A Beckman DU 7500 spectrophotometer was used to determine the maximum absorption wavelength of the dyes and
a Nicolet Magna FT-IR-750 spectroscopy apparatus was employed to determine the presence of functional groups at
room temperature. The pellets were prepared by using the
same dilution of every sample in KBr. Optical photographs
were taken with a LEICA MZ 125 stereomicroscope by region mapping (n = 6) of the sample. Quantification of the
functional groups was performed according to the Boehms
titration methodology [28] for activated carbons by using analytical grade reagents.
Adsorption isotherms were measured at a room temperature (25 C). A definite amount of adsorbent was introduced
into polycarbonate cylindrical cells with a lid, and placed in
contact with a measured volume of the aqueous dye solutions
of a known concentration in the range 0.53.0 mM. The mass
to volume relation was 1:50. After stirring for 1 h, the dye solution that resulted from the adsorption equilibrium was separated from the exhausted adsorbent after 24 h and analyzed
by high performance liquid chromatography (HPLC). The
chromatographic system consisted of a Model Constametric
I pump (LDC/Milton Roy), a Model 7125 syringe loading
sample injector (Rheodyne) with a 20 l loop and a Model
994 programmable photodiode array detector (Waters) operated at max for each dye. The chromatographic analysis [29]
was performed on Beckman and Dionex columns: Ultrapore
Octyl (7.5 cm 4.6 mm i.d.) for the BB41 dye solution, OmniPac PCX500 (25 cm 4 mm i.d.) for AB74 and Ultrasphere
Octyl (15 cm 4.6 mm i.d.) for the RB5 dye. The equilibrium
concentrations of adsorption were determined by interpolating in the following calibration curves: CBB41 = Ap /989,949
(R2 = 0.9976) at 615 nm, CAB74 = Ap /516,203 (R2 = 0.9996)
at 609 nm and CRB5 = Ap /857,428 (R2 = 0.9783) at 600 nm,
where C is the concentration of the corresponding dye solution, Ap is the area of the chromatographic peak and R2 is

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

109

Table 2
Studied dyes, their formulae, codes used in this work and calculated molecular areas

Basic blue 41 (BB41)

2
472 A

Acid blue 74 (AB74)

2
329 A

the correlation coefficient of the adjusted calibration curve.

Mobile phase composition was methanolbuffer. The mobile
phase was prepared by mixing methanol and buffer solution
KH2 PO4 Na2 HPO4 with pH 5 for BB41 (50% methanol)
and for RB5 (25% methanol). AB74 was analyzed with the
mobile phase composed by 15% acetonitrile and 85% water
(50 mM KCl + 25 mM HCl). Flow rate was 0.8 ml min1 and
analysis was performed at ambient temperature. Methylene
blue solutions used in the determination of the relative specific area were chromatographed at 660 nm with an ISCO
QA (25 cm 5 mm i.d.) column by using 50% methanol in
2 [30]
water as mobile phase. A molecular area value of 98 A
considering a dye monomer was taken. Molecular areas of
the dyes (presented in Table 2) and molecules models sized
by charge were obtained after minimization and conformational analysis, by the software Physical Properties! ProTM
3.27 from ChemSW Inc.

Reactive black 5 (RB5)

2
779 A

be appreciated. The porous texture of bagasse ash [11] was

revealed, for example, by scanning electron microscopy.
From the data shown in Table 1 it can be observed that for
the series SOMAP, SOMAP1 and SOMAP2, the activation
type B did not affect the magnitude of the specific surface,
while activation A more than doubled the Ssp . A likely explanation for this increment is formation of pores, which were
not necessarily observed under the optical microscope. In the
samples HELAP and SAGAP, a decrease in the Ssp magnitude was observed after activation with B. Characterization
by nitrogen adsorption did not yield feasible values of the
specific surface, since evacuation of the samples (with the
exception of HELAP1) was not feasible. On the other side,
the adsorption of the dye methylene blue as probe molecule

3. Results and discussion

3.1. Adsorbents characterization
Morphology of adsorbents prepared from waste materials
has not yet been addressed fully. Microscopy studies related
with banana and orange peels [8] served to establish changes
in the surface structure of the peels only after adsorption.
When examining by stereomicroscopy (Fig. 1) sieved
fractions (mesh 20) of SOMAP, SOMAP1 and SOMAP2
extracted from the same rough material (see Table 1), we
realized that although the activation procedure was different
(A and B), they all had a flake-like shape. The images
showed however, that the color and the contour of the flakes
changed with activation. It is true that in most cases natural
materials [710,1216,18] were dried and not subjected to
any form of pretreatment, with the exception of bagasse [11]
and cotton [17]. For this reason the effect of activation has
not been proved in the literature. As it can be appreciated
in Fig. 2A and B, HELAP suffered the major change in
form and morphology after activation, i.e. its haired rods
(Fig. 2A) became eroded flakes (Fig. 2B). The flakes of the
pair SAGAP and SAGAP1 shown in Fig. 2C and D presented
only a color change, which could be observed just looking at
them (not in the black and white photographs reported here).
At the magnification used in this figures, no pores could

Fig. 1. Optical photographs obtained by stereomicroscopy of the adsorbents

SOMAP (A), SOMAP1 (B) and SOMAP2 (C) 50.

110

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

Fig. 2. Optical photographs obtained by stereomicroscopy of the adsorbents HELAP (A), HELAP1 (B), SAGAP (C) and SAGAP1 (D).

resulted in a system closer to the systems under study in this

work. Very little has been written on texture characteristics
of non-carbonized natural adsorbents such as barley husk [7],
orange peel [9], apple pomace [10], bagasse [11], cobs [12],
palm-fruit bunch particles [1315], eucalyptus bark [16] and
coir pith [25] applied in dye adsorption. It has been shown
[8] that the specific surface of the peels of banana and orange
amounted 2124 m2 g1 , a lower value than the specific surface of the adsorbents of the series SOMAP, HELAP and
SAGAP studied here. High Ssp values (440 m2 g1 ) were exhibited by bagasse fly ash [11], while a low (1.63.9 m2 g1 )
specific surface magnitude was exhibited by the skin and pith
of sunflower stalks [18]. These values bear a resemblance to
that value (2 m2 g1 ) obtained by us for HELAP1 (Table 1)
when determination was carried out by adsorption of nitrogen
at 77 K, the regular method used in [8,11,18].
Early investigation of SOMAP2 [31] assigned IR bands
obviously to cellulose. When comparing the natural adsorbents studied here (Fig. 3) all spectra showed common bands
but also some difference and were reproducible from lot to
lot. Here all samples presented the 1062 cm1 band of the
C O deformation vibrations in cellulose and the shoulder
at 2940 cm1 corresponding to the C H stretching vibration. The characteristic bands of methylcellulose at 1460 and
1648 cm1 exhibited different intensity. The broad band of
the OH stretching vibration mode at 31003700 cm1 comprises both free and hydrogen bonded hydroxyl groups. The
band at 1252 cm1 appeared clearly only in the adsorbents
SOMAP, SOMAP1, SOMAP2, HELAP and HELAP1 indicating the presence of carboxylic groups. The FTIR spectrum
of all samples showed absorbance in the 10501290 cm1
region due also to the vibration of the C O group in lactones, whereby SAGAP and SAGAP1 presented defined
bands at 1160 and 1100 cm1 assigned to C O vibration of
alkylethers. SOMAP and SOMAP1 presented a broad band at

760500 cm1 , similar as that presented in the sodium phosphate salt of cellulose. Spectroscopy is usually considered a
tool just confirming the structure of synthetic adsorbents, but
also verifying the presence of functional groups introduced
by modification as for example the crosslinking of starch [32].
However, it has not been applied in any of the studies we reviewed describing the application of wastes in the adsorption
of dyes. The exception is represented by bagasse fly ash [11],
for which the presence of calcium silicate was demonstrated
by IR spectroscopy.
Although no marked differences could be observed in the
FTIR spectra of the bulk samples, a variation in the surface
chemistry could be expected after activation, as it was viewed

Fig. 3. FT-IR spectra of the adsorbents SOMAP (1), SOMAP1 (2), SOMAP2
(3), HELAP (4), HELAP1 (5), SAGAP (6) and SAGAP1 (7).

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

111

Table 3
Functional groups on the surface of the studied adsorbents quantified by Boehms titration in millimoles per gram of adsorbent and in percentage (in parentheses)
Adsorbent

SOMAP
SOMAP1
SOMAP2
HELAP
HELAP1
SAGAP
SAGAP1
Carbon
Bone black

Basic groups nOH (mmol g1 )

0.15 (8.2)
0.05 (2.6)
0.12 (12.8)
0 (0)
0.10 (5.6)
0 (0)
0 (0)
0.10
1.40

Acidic groups nH (mmol g1 )

Total amount of groups

Carboxylic

Lactonic

Phenolic

Total

mmol g1

mol m2

0.40 (22.0)
0.05 (2.6)
0.10 (10.6)
0.37 20.9)
0.25 (14.1)
0 (0)
0 (0)
0.05
0.25

0.07(3.8)
0.50 (26.3)
0.05 (5.3)
0.33 (18.6)
0.32 (18.1)
0.30 (23.1)
0.40 (36.4)
0.05
0.05

1.20(65.9)
1.30 (68.4)
0.67 (71.3)
1.07 (60.4)
1.10 (62.1)
1.00 (76.9)
0.70 (63.6)
0.40
0.20

1.67
1.85
0.82
1.77
1.67
1.30
1.10
0.50
0.50

1.82
1.90
0.94
1.77
1.77
1.30
1.10
0.60
1.90

43.3
47.5
10.4
29.5
35.4
20.0
36.7

in the morphology (Figs. 1 and 2). All the samples maintained their functional groups in the bulk after activation with
the exception of SOMAP2 (Fig. 3, line 3), where the band
at 760500 cm1 disappeared. The results of the Boehms
titration gathered in Table 3 confirmed the absence of carboxylic groups on the surface of the adsorbents SAGAP and
SAGAP1, as it was found by FTIR spectroscopy. As shown
from the titration with base, all samples were predominantly
acidic. Moreover, the sample SAGAP indicated absence of
basic groups before and after activation, and lack of carboxylic groups. Among the oxygen-containing groups, the
phenolic acidic functionality was the most abundant in all
samples and made the main contribution to the acidic surface groups. The density of the total acidic groups was similar in the pairs SOMAPSOMAP1, HELAPHELAP1 and
SAGAPSAGAP1, which represented samples before activation and after activation with B. The contrary case was
observed with the pair SOMAPSOMAP2, where the activation A produced a decrease of 50% of the acidic groups. For
comparison, titration of two carbon samples with opposite
basic character and identical total acidic groups was accomplished. The total amount of surface groups (1.90 mmol g1 )
of the bone black sample (Table 3) used commonly for decolourisation was similar to that of the natural adsorbents
SOMAP, SOMAP1 and HELAP studied in this work. Interestingly, their total amount of groups was less than that
present in wood and mineral carbon reported in [28] to test
the Boehm titration. From the penultimate column in Table 3,
it did not turn out to be clear the effect of activation on the
total amount of surface groups, since after activation the specific area changed (see Table 1). The specific density of total
functional groups in mol m2 calculated in the last column
showed that activation B increased the total number of surface
groups, while activation A produced a different result.

AB74 < BB41. Investigations on the adsorption of RB5 in

mixture with other dyes have been carried out by using corncob and barley husk [7], apple pomace and wheat straw
[10] in a concentration range 10 times smaller than the
one studied in our work. One component aqueous solutions
of RB5 (0.10.5 mM) and BB41 (0.14 mM) were studied on the adsorbents prepared from eucalyptus bark [16]
and from linseed cake [6], respectively. Considering the effect of activation on adsorption of the basic dye BB41, one
can distinguish in Table 4 that the relative saturation in
each adsorbent series was: SOMAP2 < SOMAP1 < SOMAP,
HELAP < HELAP1 and SAGAP < SAGAP1, indicating that
activation B produced an increment in the saturation capac-

3.2. Adsorption interaction

From the curves in Fig. 4 the trend of adsorption was
RB5 < AB74 < BB41. The saturation capacity am listed in
Table 4 confirmed that adsorption of the reactive dye RB5
from water solution occurred in a lesser extent in comparison with the basic (BB41) and acid (AB74) dyes, whereby

Fig. 4. Adsorption isotherms of the basic dye BB41 (A), the acid dye AB74
(B) and the reactive dye RB5 (C) by the adsorbents SOMAP ( ), SOMAP1
(
), SOMAP2 (), HELAP (), HELAP1 (), SAGAP () and SAGAP1
().

112

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

Table 4
Adsorption parameter values of the calculated monolayer capacity am (mol m2 ) in the Langmuir adsorption isotherm equation (a = (am kL C)/(1 + kL C)),
of the heterogenity degree 1/n in the Freundlich equation (a = kF C1/n ) and of the coverage degree = amax /am
Adsorbent

Basic blue 41
am

1/n

SOMAP
S0MAP1
SOMAP2
HELAP
HELAP1
SAGAP
SAGAP1

3.3
3.0
2.7
2.3
2.6
2.0
3.0

0.48
0.35
0.69
0.48
0.38
0.89
0.37

0.82
0.91
0.55
0.85
0.92
0.79
0.83

Acid blue 74
am

1/n

1.4

0.1
0.2
0.6

0.7

0.22
1.06
0.47
0.50
0.22
1.24
0.37

ity of the adsorbents of the series HELAP and SAGAP. For

SOMAP activator A generated a decrease due to the fall in
the number of functional groups on the surface as it was
discussed in Table 3. The adsorption isotherms presented a
Langmuirian character, with the exception of dye AB74 on
the adsorbents SOMAP1 and SAGAP. The adsorption of this
acid dye on SOMAP doubled practically the adsorption extent, which can be achieved on the other adsorbents until their
theoretical saturation. Also SOMAP together with HELAP
adsorbed the reactive dye RB5 in a greater degree in comparison with the other adsorbents within this study. When
comparing the saturation capacity am of our adsorbents with
those produced by other authors, SOMAP2 exhibited upon
the BB41 dye for example, a similar capacity as linseed cake
[6] with particle diameter 355500 m. Besides the am values, Table 4 shows the surface coverage obtained in our
measurements. It varied between 0.51 and 1.04 indicating
less than a layer coverage, whereby in most of the studied
systems the coverage was 0.8 < < 0.9.
The Langmuir equation describes adsorption on strongly
homogeneous surfaces, which is not the case of natural adsorbents exhibiting first of all a chemical heterogeneity represented by the different functional groups. The Freundlich
isotherm equation considers heterogeneous surfaces and is
based on the idea that the adsorption depends on the energy
of the adsorption sites. The 1/n values of the Freundlich adsorption equation, which are summarized in Table 4 varied
from 0.22 to 1.24 revealing adsorption sites with a broad energy distribution, since the greater the difference between n
and 1, the wider is the distribution of the surface interaction
energies. On coir pith 1/n values varied for example, between
0.19 and 2.38 for acid and basic dyes [25], evidencing also
the energetical heterogenity of this natural adsorbent. The
systems, where the exponent was close to unity, but 1/n > 1,
indicated that saturation was not attained, as it was already
pointed out when the Langmuir equation was used for the
analysis of the isotherm. On the contrary, in most systems
where 1/n < 1, 1/n 0, the adsorbent was saturated with the
dye molecule since adsorption energies decreased with surface density. In view of the fact that the energetic heterogeneity could be represented by the kind and amount of functional
groups on the surface and could reproduce the 1/n values, the
distribution of the quantified groups summarized in Table 3

0.97
0.81
0.75
0.86
0.81

Reactive black 5
am

1/n

0.5
0.2
0.2
0.3
0.2
0.2
0.3

0.30
0.83
1.04
0.29
0.31
0.47
0.37

0.94
0.78
0.51
0.94
0.91
0.69
0.87

was evaluated statistically by constructing normal curves and

evaluating their variance. Fig. 5A shows that the distribution
curves for the studied adsorbents differed in amplitude and
height reflecting different heterogeneity degree. The 1/n values correlated poorly with the variance of the group distribution curves when all adsorbents were taken into account.
When the adsorbent SOMAP2 was excluded from the correlation, the fitting improved considerably (0.45 < R2 < 0.53)
as it is demonstrated in the insert in Fig. 5B. This fact reinforced the peculiarities observed for SOMAP2, which was
the single adsorbent activated with activator A.
Normally, molecular structure of a compound has a significant effect on its adsorption extent. In general, the adsorption

Fig. 5. Distribution curves of the surface functional groups on the studied

adsorbents (A), correlation between the isotherm exponent 1/n of the considered dyes and the variance of the distribution curves (B), and between
the monolayer capacity am upon the basic dye BB41 and the total amount
of acid groups on the adsorbents (C).

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

113

Fig. 6. Model depicting the interaction between dye molecules and a cellulosic surface, according to the charge in the adsorbate molecules and the surface
functional groups on the adsorbent.

potential of a molecule is enhanced by increasing molecular size and for example, aromaticity in the case of carbon.
In the case of dyes and carbon, only small molecules penetrate into micropores, whose content reduces dramatically
after thermal regeneration. The molecular area of the dyes
studied here, increases AB74 < BB41 < RB5 as it is shown
in Table 2 and did not correspond with their adsorbability
on the studied adsorbents (see Fig. 4). Hence, on natural adsorbents as SOMAP1, HELAP and SAGAP the intermolecular interactions between the functional groups of each dyes
and the surface chemistry of the adsorbents may play an
important role. To test this hypothesis, we chose precisely
adsorbates carrying diverse groups and exhibiting different
character: the cationic organic base BB41 used for acrylic
fibers, the organic acid AB74 that associates with nitrogenous basic groups in wool and the reactive molecule RB5
that bonds with the fibers by addition method. The values
presented in Table 3 demonstrated that acidic groups prevailed over basic groups on the surface of the studied adsorbents. This explained the higher adsorption values of the
basic dye BB41 in comparison with the acid dye AB74, due to
the electrostatic interactions depicted schematically in Fig. 6.
Furthermore, the calculated monolayer capacity of all studied adsorbents upon the basic dye BB41 correlated acceptably (R2 = 0.8599) with the corresponding amount of total
acid groups nH as it can be seen in Fig. 5C. Examining the
positive charge on the basic dye molecule interacting with
the negatively charged surface, it was not surprising why for
example HELAP (without basic groups) adsorbed the basic
BB41. Looking at the concentration of basic and acid groups
in the SOMAP adsorbent series in Table 3, it will be useful to
examine the adsorption isotherms of the acid dye (Fig. 4B),
where SOMAP (nOH = 3.6 mol m2 ) occupied the upper
position, SOMAP1 (nOH = 1.2 mol m2 ) the intermediate
and SOMAP2 (nOH = 1.3 mol m2 ) the lowest. This corresponded approximately to the surface amount of basic groups
(nOH , in mol per square meter). SOMAP1 and SOMAP2

presented similar amount of basic groups and very different surface concentration of acid groups. This fact can explain probably the form of the SOMAP1 adsorption isotherm,
which at low concentrations suggested low affinity as a result of the repulsion produced by the high amount of acid
groups (46.2 mol m2 ) in comparison with 9.1 mol m2
in SOMAP2. The attraction of cationic dye bases by anionic
cellulosic structures has already been mentioned [15], but
not demonstrated quantitatively. Qualitative mechanisms for
the adsorption interaction of acid dyes have been presented
for modified silica [5] and cotton [17]. In spite of the cellulosic character of the studied adsorbents, the low adsorption
of the reactive dye RB5 used in dyeing of cellulosic fibers
could be due to the absence of mediators and conditions favoring the reaction between the dye and the specific sites
on the adsorbent surface. Judging in general from the adsorption magnitudes depicted in the adsorption isotherms in
Fig. 4 and the calculated monolayer values listed in Table 4,
the high adsorption capacity of the studied solids under the
given conditions cannot be declared. However, a visible and
considerable decolourisation of the dye solution at the given
concentration was observed. Comparable adsorption (98%)
of the RB5 dye could be achieved on SOMAP2 and carbon from 400 mg l1 solutions [26] by using a 1:10 mass to
volume relation, while SOMAP1s efficiency reached 60%
upon RB5 and 98% upon BB41. As known, and precisely
demonstrated for the adsorption of RB5 on different natural
adsorbents [7,10,16]; dye and adsorbent concentration have
the most significant influence on the adsorption magnitude.
Concluding this section, we can say that the present part
of this study served to demonstrate qualitatively and semiquantitatively the role of the physicochemical interactions
between dyes and adsorbents. By considering the coverage
degree reached in each system (see Table 4) a model depicting quantitatively the surfacedye interaction could be
proposed. However, any model, which does not take into account the orientation and aggregation of the dye molecules

114

M.M. Davila-Jimenez et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 254 (2005) 107114

in solution would be incomplete, but it is within the scope of

a future study.

4. Conclusions
The present study showed that natural adsorbents prepared
from maize waste might be characterized. According to the
composition, texture, and surface chemistry, the adsorption
potential of a natural maize waste product can be evaluated.
Our results demonstrated the important role of the surface
chemistry, contrary to the leading function of the magnitude
of the specific surface. The characterization of non-expensive
solids prepared and adapted from natural agricultural wastes
will help customize dyeadsorbent interactions and therefore, optimize adsorption efficiency for environmental applications.

Acknowledgement
AAPC thanks CONACyT for a scholarship grant
(130497).

References
[1] M.M. Nassar, M.S. El-Geundi, J. Chem. Tech. Biotechnol. 50 (1991)
257.
[2] K.R. Ramakrishna, T. Viraraghavan, Water Sci. Technol. 36 (1997)
189.
[3] O.J. Hao, H. Kim, P.-Ch. Chiang, Crit. Rev. Environ. Sci. Technol.
30 (2000) 449.
[4] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Bioresour. Technol. 77 (2001) 247.
[5] A. Krysztafkiewicz, S. Binkowski, T. Jesionowski, Appl. Surf. Sci.
199 (2002) 31.

[6] R.M. Liversidge, G.J. Lloyd, D.A.J. Wase, C.F. Forster, Process
Biochem. 32 (1997) 473.
[7] T. Robinson, B. Chandran, P. Nigam, Environ. Int. 28 (2002)
29.
[8] G. Annadurai, R.-Sh. Juang, D.-J. Lee, J. Hazard. Mater. B92 (2002)
263.
[9] R. Sivaraj, C. Namasivayam, K. Kadirvelu, Waste Manage. 21 (2001)
105.
[10] T. Robinson, B. Chandran, P. Nigam, Water Res. 36 (2002) 2824.
[11] V.K. Gupta, D. Mohan, S. Sharma, M. Sharma, Sep. Sci. Technol.
35 (2000) 2097.
[12] M.S. El-Geundi, Water Res. 25 (1991) 271.
[13] M.M. Nassar, M.F. Hamoda, G.H. Radwan, Water Sci. Technol. 32
(1995) 27.
[14] M.M. Nassar, Y.H. Magdy, Chem. Eng. J. 66 (1997) 223.
[15] M.M. Nassar, Water Sci. Technol. 40 (1999) 133.
[16] L.C. Morais, O.M. Freitas, E.P. Goncalves, L.T. Vasconcelos, C.G.
Gonzalez Beca, Water Res. 33 (1999) 979.
[17] I. Bouzaida, M.B. Rammah, Mater. Sci. Eng. C21 (2002) 151.
[18] G. Sun, X. Xu, Ind. Eng. Chem. Res. 36 (1997) 808.
[19] W.T. Tsai, C.Y. Chang, S.L. Lee, Carbon 35 (1997) 1198.
[20] W.T. Tsai, C.Y. Chang, S.L. Lee, Bioresour. Technol. 64 (1998)
211.
[21] F.C. Wu, R.L. Tseng, R.S. Juang, Environ. Technol. 22 (2001)
205.
[22] C. Namasivayam, D. Kavitha, Dyes Pigments 54 (2002) 47.
[23] C. Namasivayam, M.D. Kumar, K. Selvi, R.A. Begum, T. Vanathi,
R.T. Yamuna, Biomass Bioenerg. 21 (2001) 477.
[24] P.K. Malik, Dyes Pigments 56 (2003) 239.
[25] F.Ch. Wu, R.-L. Tseng, R.-Sh. Juang, J. Hazard. Mater. 69 (1999)
287.
[26] M.P. Elizalde-Gonzalez, A.A. Pelaez-Cid, Environ. Technol. 24
(2003) 821.
[27] M.M. Davila, M.P. Elizalde, A.A. Pelaez, Patent in preparation.
[28] I.I. Salame, T.J. Bandosz, J. Colloid Interf. Sci. 240 (2001) 252.
[29] M.M. Davila-Jimenez, M.P. Elizalde, A. Gonzalez, A.A. GutierrezGonzalez, Pelaez-Cid, J. Chromatogr. A 889 (2000) 253.
[30] N.V. Keltsev, Teoreticheskie Osnovy Adsorbtsionnoi Tekhniki,
Khimiya, Moscow, 1976.
[31] A.A. Pelaez-Cid, M.Sc. thesis, UAP, Mexico, 2001.
[32] F. Delval, G. Crini, N. Morin, J. Vebrel, S. Bertini, G. Torri, Dyes
Pigments 53 (2002) 79.