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Bioresource Technology xxx (2007) xxx–xxx

Short Communication

Chemically modified maize cobs waste with enhanced

adsorption properties upon methyl orange and arsenic
a,*
Marı́a P. Elizalde-González , J. Mattusch b, R. Wennrich b

a
UAP – Universidad Autónoma de Puebla, Instituto de Ciencias, Centro de Quı́mica, Apdo. Postal J-55, Puebla 72571, Pue, Mexico
b
Helmholtz Centre for Environmental Research, UFZ, Department of Analytical Chemistry, Permoserstr. 15, 04318 Leipzig, Germany

Received 2 May 2006; received in revised form 5 September 2007; accepted 10 September 2007

Abstract

The surface chemistry of maize naturasorbent was altered in this work by the modifying agents: phosphoric acid and different amines
(triethanolamine, diethylenetriamine and 1,4-diaminobutane). Removal of methyl orange (25 mg l1) was <50% by maize corn cobs
modified by phosphorylation and higher by the quaternized samples: 68% with the 1,4-diaminobutane and 73% with the diethylenetri-
amine modificators. Adsorption of arsenite by the samples modified with phosphoric acid/ammonia was 11 lg g1, which corresponds to
98% removal from a 550 lg As l1 solution for an adsorbent dose of 50 mg ml1. The samples modified by phosphoric acid/urea
removed 0.4 lg g1 arsenate from a 300 lg As l1 solution. Adsorption of methyl orange, arsenite and arsenate was superior by the
chemically modified maize cobs judged against the initial naturasorbent. For comparison, removal by the commercial anion exchanger
was 100% for methyl orange, 45% (5 lg g1) for arsenite and 99% (5 lg g1) for arsenate.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Methyl orange; Arsenic; Maize; Chemical modification

1. Introduction topic of environmental investigation due to their low cost

Arsenic occurs in surface and in ground waters and its
presence has been associated with arsenical dermatitis
and skin cancer. In potable water supplies (Badruzzaman
et al., 2004) arsenic usually arises as arsenate As(V) or arse-
nite As(III) in different anionic forms depending on pH. In
neutral form, not dissociated arsenate (H3AsO4) prevails at
pH < 2, while arsenite (H3AsO3) exists only at pH < 9. We
have studied the adsorption of arsenic on natural zeolites
(Elizalde-González et al., 2005). Additionally, anion
exchange resins have been used for arsenic species separa-
tion (Pohl and Prusisz, 2004) and for water treatment
(Korngold et al., 2001; Vaaramaa and Lehto, 2003). In
recent years, development of adsorbents obtained from
naturally occurring materials and wastes has become a
*
Corresponding author. Tel.: +52 222 229 5500; fax: +52 222 229 5525.
E-mail address: melizald@siu.buap.mx (M.P. Elizalde-González).
and biodegradability (Elizalde-González, 2006).
Most agricultural wastes are cellulose based and since
the surface of cellulose immersed in water is negatively
charged, the proper approach for adsorption of negatively
charged species, as those corresponding to acid dyes and
the arsenic species (H2 AsO 3, HAsO2 3 , H2 AsO4,
2 3
HAsO4 , AsO4 ), is modification of the surface. Several
natural materials have been subjected to chemical modifi-
cation, including sunflower stalks (Shi et al., 1999), sawdust
(Baouab et al., 2001), orange waste (Ghimire et al., 2003),
peanut hull (Gong et al., 2005), soybean hulls, sugarcane
bagasse and corn stover (Marshall and Wartelle, 2004;
Wartelle and Marshall, 2005). Chemical modification
methods tested so far on agricultural residues have been
developed to improve adsorption of acid dyes. For arsenic,
the removal of As(III) and As(V) from water by direct
application of pulverized hyacinth roots without modifica-
tion was demonstrated (Al Rmalli et al., 2005) and tested
on gels prepared from iron-modified orange peel (Ghimire

0960-8524/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.09.023

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2 M.P. Elizalde-González et al. / Bioresource Technology xxx (2007) xxx–xxx

et al., 2003). The objective of this work was the application
of different modification reactions to maize waste in order
to enhance its ability to adsorb arsenite, arsenate, and
methyl orange as an anionic azo dye representative.
2. Experimental
2.1. Materials
The adsorbent materials designated as SOMAP and its
activated form SOMAP1 were obtained from maize cobs
(Elizalde-González and Peláez-Cid, 2003), characterized
and used in the adsorption of basic and reactive dyes (Dáv-
ila-Jiménez et al., 2005). Chemical modification reactions
are summarized in Tables 1 and 2.
The following analytical grade reagents were used in this
work: cellulose propionate (CP) (Aldrich), diethylamino-
ethylcellulose (DAC), urea, 1,4-diaminobutane (DAB)
from Merck; triethanolamine (TEA), and diethylenetria-
mine (DETA) from Fluka. For samples M-P1 and M-P2
a volume of 50 ml H3PO4 containing SOMAP, reacted by
dropwise addition of 50 ml urea or NH4. For M-P3 and
M-P4 a volume of 400 ml of H3PO4 containing SOMAP1
was stirred with 100 ml urea or NH4, respectively. The
resulting solid phase was decanted. To prepare adsorbents
containing quaternary ammonium groups, 50 ml of 1 mM
solutions were stirred with SOMAP1. In every procedure
the product was filtered, washed with deionised water to
realize pH 5.0, afterwards filtered again and dried at
60 C. Stock solutions of varying concentrations of the
individual arsenic compounds were prepared from As2O3
(Fluka, Buchs, Switzerland) to obtain As(III) solution
and the As(V) solution was Titrisol (Merck). All solutions
were prepared using deionised water (Milli-Q, Millipore).
Methyl orange (MO) was purchased from Aldrich.
2.2. Methods
Organic elemental analysis was performed with a CHN
1000 Leco elemental analyzer calibrated with SRM 1571
orchard leaves (NIST). The oxygen content was obtained
indirectly by difference. An automated adsorption appara-
tus (Quantachrome/Autosorb-1) was used for the measure-
ment of N2 adsorption isotherms at 77 K and for the
determination of the specific surface Ssp. The basicity of
the modified adsorbents was determined by mixing 0.25 g
of each sample with 25 ml of 30 mM HCl solution in a stir-
red flask for 48 h at room temperature. Then the liquid was
decanted and the equilibrium HCl was titrated with 3 mM
NaOH. Adsorption was measured as described (Elizalde-
González et al., 2005) using aqueous arsenic solutions:
550 lg l1 As(III) and 300 lg l1 As(V) and equilibrium

Table 1
Adsorbents prepared by chemical modification of SOMAP and SOMAP1 for the uptake of arsenic and methyl orange
Maize adsorbent used for modification SOMAP SOMAP1
1
Initial basic groups, mmol g from Dávila-Jiménez et al. (2005) 0.15 0.05
Initial acidic groups, mmol g1 from Dávila-Jiménez et al. (2005) 1.67 1.85
Reaction type Reaction scheme representing the reactive cellulose moiety Sample code

O
OH
CH2O P
Phosphorylation CH2OH M-P1 M-P3
OH
Urea
O H3PO4 O M-P2 M-P4
NH4OH
O O

CH2OH CH2O N(CH2CH2OH)3

Quaternization M-Q1
O N(CH2CH2OH)3 O
O M-Q2
O

CH2O NH(CH2CH2NH2)2
CH2OH
M-Q3
O (NH2CH2CH2)2NH O
O O

O O
O
CH2
CH2OH
O
O NH2(CH2)4NH2 NH2(CH2)4NH2
O M-Q4
O
CH2
O
O O

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M.P. Elizalde-González et al. / Bioresource Technology xxx (2007) xxx–xxx 3

Table 2
Elemental composition and physical properties of the adsorbents prepared by chemical modification of SOMAP and SOMAP1
Sample Modification procedure and Colora Yieldb Apparent Basicity Elemental analysis (%) O
CþH  102 N
CþH  102
reaction conditions (%) density (leq g1)
C H N O
(mg ml1)
SOMAP None cw – 0.25 176 46.1 6.1 1.2 46.6 89.3 2.3
SOMAP1 Chlorinated agent cw – 0.37 50 46.4 6.0 0.5 46.9 89.4 1.2
M-P1 1 M H3PO4 + 1 M urea cw 60 0.14 6 48.1 6.0 0.9 45.0 83.2
(6 h, 90 C)
M-P2 1 M H3PO4 + NH4OH cw 73 0.10 40 47.1 5.9 0.8 46.2 87.2
(25%) (6 h, 90 C)
M-P3 1 M H3PO4 + 2 M urea cw 56 0.06 10 47.0 5.6 0.6 46.8 89.0
(2 h, 60 C)
M-P4 1 M H3PO4 + 2 M NH4OH cw 44 0.12 9 45.4 4.7 0.6 49.2 98.2
(2 h, 60 C)
M-Q1 1 mM triethanolamine b 43 0.17 47 46.7 5.9 0.7 46.7 1.3
(6 h, 90 C)
M-Q2 1 mM triethanolamine cw 78 0.23 22 46.9 5.0 0.5 47.6 1.0
(4 h, 60 C)
M-Q3 1 mM diethylenetriamine cw 86 0.22 5 46.2 5.8 0.8 47.2 1.5
(4 h, 60 C)
M-Q4 1 mM 1,4-diaminobutane cw 73 0.23 8 46.1 5.5 0.6 47.8 1.2
(4 h, 60 C)
CP Cellulose propionatec w – 0.61 34 56.4 6.5 0 37.0 58.8 –
DAC Diethylaminoethyl cellulose, w – 0.23 3 15.0 9.8 0.4 74.8 301.6 1.6
anion exchanger c
a
cw = cream white, b = brown, w = white.
b
Calculated relative to the initial mass of SOMAP.
c
Commercial, synthetic.

time of 30 days and 14 days, respectively. Quantification
was performed by atomic absorption spectrometry using
a Perkin Elmer PE 4100 ZL equipment using the combina-
tion of hydride generation and graphite furnance atomiza-
tion. Adsorption of MO (25 mg l1), pH 4.3–4.5 was
determined by VIS spectrophotometry at 463 nm by using
a Perkin Elmer Lambda 2 equipment.
3. Results and discussion
3.1. Modification with different agents
The morphology of the adsorbent particles changed
after modification, whereby a dendritic pattern could be
observed in the longed particles modified with phosphoric
acid and ammonia. Table 2 summarizes the physical char-
acteristics of the adsorbents prepared by modification. For
comparison, CP and the commercial anion exchanger DAC
were characterized and tested. In general, a drastic decrease
of the material apparent density was noticed after modifi-
cation and in some cases also a color change. Measure-
ments of Ssp did not show significant differences among
replicates and between samples modified by diverse reac-
tions. This was due to the extremely low magnitude exhib-
ited by the original maize corn cob sample SOMAP
(Ssp  1 m2 g1).
The elemental composition of the resulting sorbents is
presented in Table 2 together with the oxygen to car-
bon + hydrogen O/(C + H) ratio for the phosphorylation
reactions and the nitrogen to carbon + hydrogen N/
(C + H) ratio for the quaternization. The important infor-
mation is the nitrogen content (1.2%) in the raw SOMAP
material proceeding probably from the maize amino acids.
The O/(C + H) ratio was considered to estimate the degree
of phosphorylation since the introduced phosphorous
groups had an oxygen-enrichment effect on the total com-
position. In the starting material SOMAP, O/(C + H) was
89.3 · 102 and decreased in M-P1 and M-P2 indicating
that the phosphoric acid used in the modification presented
a leaching artifact on the SOMAP matrix. The O/(C + H)
ratio in SOMAP1, taken in the preparation of M-P3 and
M-P4 was 89.9 · 102 (Elizalde-González et al., 2006)
and it exhibited a similar (in M-P3) and larger (in M-P4)
value in the modified samples. Increasing the ammonia or
urea concentration led to elevated amounts of oxygen
introduced into the modified adsorbents, since the O/
(C + H) ratios increased from 83.2 to 98.2 · 102 (see
Table 2). Reaction with TEA at different temperature indi-
cated that higher temperatures yielded greater N/(C + H)
ratios in samples M-Q1 and M-Q2. However, a high reac-
tion temperature (180 C), as that employed (Wartelle and
Marshall, 2005) for the modification of sugarcane and soy-
bean hulls, would led to carbonization of the studied maize
adsorbent.
The N/(C + H) ratio in the starting material SOMAP
was 2.23 · 102, almost 50% higher than in the synthetic
cellulose DAC (1.6 · 102), in which nitrogen came
directly from the modifying amine. In SOMAP1, used in
the preparation of the quaternized samples, the N/
(C + H) ratio was 1.2 · 102. By using this value as refer-

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4 M.P. Elizalde-González et al. / Bioresource Technology xxx (2007) xxx–xxx

ence, it can be estimated that the largest modification highest adsorption of MO was achieved with the samples
degree was achieved by M-P3 (see Table 2). This was con- M-Q3 (73%) and M-Q4 (68%), which exhibited the lowest
gruent with the nitrogen content in the modificator accord- basicity in the series of the modified adsorbents (see Table
ing to the series: DETA > DAB > TEA and the 2), being very close to the basicity of the anion exchanger
corresponding nitrogen relative concentration in the sam- DAC. This result suggests that the MO species interacted
ples: M-Q3 > M-Q4 > M-Q2. The samples M-Q1 and M- electrostatically with the quaternized surface of SOMAP.
Q2 prepared using the same modificator showed different Although basicity and nitrogen content of the M-Q3 sam-
nitrogen content, resulting from the dissimilar reaction ple and the synthetic anion exchanger DAC were similar,
conditions. The nitrogen composition of samples M-P1 M-Q3 did not yield total removal of MO, as DAC did,
and M-P2 was comparable with the nitrogen content due probably to the structure of the modifying moiety on
reached after modification of sugarcane bagasse with dim- the surface of the modified SOMAP.
ethyloldihydroxyethylene urea but lower than in soybean
hulls and corn stover (Wartelle and Marshall, 2005). 3.3. Adsorption of arsenite
The reaction between hydroxyl groups of the cellulosic
adsorbent SOMAP and the nitrogen containing com- The adsorption of As(III) was measured on two samples
pounds to yield quaternary nitrogen groups could be pre- modified by phosphorylation and one quaternized SOMAP
sumably confirmed by IR spectroscopy. The FTIR adsorbent. From the amounts adsorbed by modified sam-
spectra of the quaternized samples and of the commercial ples of SOMAP presented in Fig. 1b, it can be seen that
DAC showed absorption bands at 3200 cm1 (mN–H) and the sample M-P2 exhibited the highest efficiency, even if
at 1052 cm1 (mC–N), which did not become stronger in one considers the anion exchanger DAC with 45%
the M-Q1–M-Q4 modified samples. Differences in the spec- removal. Inspite of setting in all the measured systems an
tra were not remarkable due to overlapping of the bands identical initial pH (7.5) of the As(III) solution, when the
existing in the not modified sample SOMAP1. However, adsorption equilibrium concentration of As(III) was mea-
the diminution observed in the C–O bands at 1730 and sured, the systems under question had respectively, final
1242 cm1 could support the occurrence of modification. pH 5.0 and 9.2 (see Table 3). This last value coincided with
Several weak bands for N–H vibrations corresponding to the pK1 = 9.2 of the equilibrium H3 AsO3 $ H2 AsO 3.
1
quaternized amino groups R2 NHþ 2 (2800–2000 cm ) and Thus, adsorption of As(III) occurred in a not dissociated
+ 1
R3NH (2700–2250 cm ) could also be observed in form both in presence of M-P2 and DAC, whereby an
DAC and in the modified samples. anion exchange mechanism for the retention of As(III)
could not be favoured. Among the samples subjected to
3.2. Adsorption of methyl orange phosphorylation, M-P1 and M-P2, which were obtained
under the same conditions and different neutralizing agent,
As example for adsorption of an anionic compound on modification occurred in different extent as seen by the O/
modified maize adsorbents, MO was used. This probe mol- (C + H) ratio (see Table 2).
ecule is acidic (pKa 3.39) and allows the visualization of the The characterization of the acidic–basic properties of
adsorption process. MO, as monosulfonic acid, exhibits an the modified adsorbents helped to understand the adsorp-
intermediate dissociation constant with respect to As(III) tion results. The extremely low adsorption of As(III) by
and As(V): greater than the first dissociation constant of SOMAP was due to the high amount of acidic groups
arsenate H3 AsO4 ƒƒƒ
pK 1 ¼2:19
ƒ! H2 AsO þ (890 leq g1) generating repulsion. The maximum adsorp-
4 þH and lower than
pK 1 ¼9:20 tion efficiency (11.4 leq g1) was obtained by the sample
that of of arsenite H3 AsO3 ƒƒƒ ƒ! H2 AsO þ
3 þ H . Fig. 1a M-P2, which exhibited the highest amount of basic groups
shows the level of adsorption of MO by the different mod-
(40 leq g1), and a small amount of acidic groups
ified adsorbents at the adsorption equilibrium pH value of
(2.3 leq g1).The adsorption of arsenic (in competitive
4.5, which prevailed in all the systems containing MO. The
conditions with chromium and selenium) has already been
reported for corn stover modified with dimethyloldihydr-
oxyethylene urea and choline chloride (Wartelle and Mar-
99

a b c
98

100 12 6
Removal, %

99

shall, 2005). However, it led only to a removal of 23% using

73

a, μg g-1

80
68

60 8 4 a 500 lg l1 arsenic solution. In our study, the calculated

45

45

40 As(III) removal by 100 mg of M-P2 reached 98% from a

27
22

4 2
20
15

20
100 lg l1 solution.
7

M-P3 9

9
M-P2 6
SOMAP 3

M-Q3 3
SOMAP 3

0 0 0
SOMAP
M-P2
M-P3
M-P4
M-Q2
M-Q3
M-Q4
DAC

M-P1
M-P2

M-Q1

DAC

DAC
CP

3.4. Adsorption of arsenate

Fig. 1. Comparison of the removal of (a) MO (25 mg l1), (b) arsenite
From the materials listed in Table 2, two samples mod-
(550 lg l1), and (c) arsenate (300 lg l1) from solutions in contact with
modified SOMAP samples at 24 C after 15 days using adsorbent dosage ified by phosphorylation and one prepared by chemical
60 mg ml1 (a), 10 mg ml1 (b) and 50 mg ml1 (c). Above the bars modification with DETA were also tested for As(V)
removal percent respective to the initial concentration. adsorption at an identical initial pH of 5.4. To compare

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M.P. Elizalde-González et al. / Bioresource Technology xxx (2007) xxx–xxx
Table 3
Final pH values of solutions of arsenite and arsenate after uptake by modified SOMAP adsorbents
pHi SOMAP M-P1
a
Arsenite H3AsO3 7.6 5.4 6.0
Arsenate H2 AsO
4 5.4a 5.8
a
Measured as aqueous KCl solutions.
b
Existing species: HAsO2
4 .
the results with modified and not modified cellulose, As(V)
tests were performed both on synthetic DAC and CP,
which did not contain nitrogen. Adsorption of As(V) was
superior on DAC than on any of the prepared samples
M-P2, M-P3 and M-Q3 as illustrated in Fig. 1c. The mate-
rial M-Q3 with the highest N/(C + H) ratio, which also
removed well the MO dye, showed poor efficiency for
As(V) although its relative nitrogen content was similar
to that of DAC (see Table 2).
According to the observed pH value at adsorption equi-
librium (see Table 3), the prevailing As(V) species adsorbed
in this work was H2 AsO 4 (pK1 = 2.19) in the systems con-
taining SOMAP, M-P2, M-P3 and DAC, and HAsO2 4
(pK2 = 6.94) in the solutions containing M-Q3 and CP. A
possible explanation for the low As(V) adsorption effi-

ciency could be repulsion between H2 AsO 4 and M-P2
 MPEG is thankful to the Alexander von Humboldt
or M-P3 at acidic pH, and unfavorable steric position
of quaternary nitrogen sites in M-Q3 for the adsorption
of HAsO2 4 at pH 7. In contrast, DAC with similar quater-
nary nitrogen content as M-Q3 adsorbed well H2 AsO 4 at
pH 5.6.
Not considering maximum uptake from monolayer
capacity, reports concerning adsorbed amounts of arsenic
diverge considerably. This depends on several factors such
as the initial arsenic concentration, the nature of the adsor-
bent, the pH values, the adsorbent dose, temperature and
equilibrium time. Iron and aluminium related solids are
known efficient adsorbents for arsenic removal. Data
reported as ‘‘high’’ removal percent (>98%) of As(V) and
recalculated as adsorbed amounts were 6 lg g1 on Fe3+
impregnated granular activated carbon (Mondal et al.,
2006), 50 lg g1 on modified calcined bauxite (Bhakat
et al., 2006), and 500 lg g1 on an anion exchanger pre-
pared from coconut coir pith (Anirudhan and Unnithan,
2007). The following adsorption capacity of natural wastes
can be found in the literature: 1.6–3.1 mg As g1 on acti-
vated carbon produced from oat hulls (Chuang et al.,
2005), 3 mg As g1 on pulverized hyacinth roots without
modification (Al Rmalli et al., 2005), and 10 mg As(III)
g1 on gels prepared from iron-modified orange peel (Ghi-
mire et al., 2003). This report presents preliminary results
and further work is being performed to enhance adsorption
of arsenic species on modified cobs.
4. Conclusions
Modification of environmental friendly adsorbents
obtained from maize waste can be achieved with phospho-
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Technol. (2007), doi:10.1016/j.biortech.2007.09.023
5
M-P2 M-P3 M-Q1 M-Q3 DAC CP
5.0 6.0 9.2
5.9 6.3 7.0b 5.6 7.0b
ric acid and nitrogen containing substances. Reaction con-
ditions applied in the phosphorylation and quaternization
using similar modificators affected respectively, the oxygen
and nitrogen content of the resulting samples. Reactions
with amines enhanced substantially the removal of methyl
orange by modified samples in comparison with the origi-
nal maize samples. A given procedure leading to the mod-
ification of the content of basic groups, positive charges or
electron acceptor moieties is not universal for the interac-
tion with anionic species. Modification can be optimized
in order to increase the adsorption of arsenite and arsenate
by chemically modified maize cobs.
Acknowledgement
Foundation (Germany) for a research grant (2005).
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Please cite this article in press as: Elizalde-González, M.P. et al., Chemically modified maize cobs waste with enhanced ..., Bioresour.
Technol. (2007), doi:10.1016/j.biortech.2007.09.023