Environ. Sci. Technol.
2003, 37, 4449-4456
Removal of Hexavalent Chromium
from Wastewater Using a New
Composite Chitosan Biosorbent
V E E R A M . B O D D U , * ,†,|
K R I S H N A I A H A B B U R I , ‡,§
JONATHAN L. TALBOTT,‡ AND
E D G A R D . S M I T H †,‡,|
U.S. Army Construction Engineering Research Laboratories,
Champaign, Illinois 61826-9005, and Illinois Waste
Management and Research Center, Illinois Department of
Natural Resources, University of Illinois at
UrbanasChampaign, Champaign, Illinois 61820
A new composite chitosan biosorbent was prepared by
coating chitosan, a glucosamine biopolymer, onto ceramic
alumina. The composite bioadsorbent was characterized
by high-temperature pyrolysis, porosimetry, scanning electron
microscopy, and X-ray photoelectron spectroscopy.
Batch isothermal equilibrium and continuous column
adsorption experiments were conducted at 25 °C to evaluate
the biosorbent for the removal of hexavalent chromium
from synthetic as well as field samples obtained from chrome
plating facilities. The effect of pH, sulfate, and chloride
ion on adsorption was also investigated. The biosorbent
loaded with Cr(VI) was regenerated using 0.1 M sodium
hydroxide solution. A comparison of the results of the
present investigation with those reported in the literature
showed that chitosan coated on alumina exhibits greater
adsorption capacity for chromium(VI). Further, experimental
equilibrium data were fitted to Langmuir and Freundlich
adsorption isotherms, and values of the parameters of the
isotherms are reported. The ultimate capacity obtained
from the Langmuir model is 153.85 mg/g chitosan.
Introduction
Process waste streams from mining operations, metal-plating
facilities, power generation facilities, electronic device manu-
facturing units, and tanneries often contain metal ions at
concentrations above local discharge limits. These waste
streams contain toxic heavy metals such as chromium,
cadmium, lead, mercury, nickel, and copper. Groundwater
around many mining, plating, and processing industries,
nuclear fuel complexes, and military bases often gets
contaminated with hazardous components. To meet envi-
ronmental regulations, effluents or water contaminated with
heavy metals must be treated before discharge. Chemical
precipitation, oxidation/reduction, mechanical filtration, ion
exchange, membrane separation, and carbon adsorption are
among the variety of treatment processes widely used for
the removal of toxic heavy metals from the waste streams.
* Corresponding author phone: (217)398-5511; fax: (217)373-3430;
e-mail: veera.boddu@erdc.usace.army.mil.
† U.S. Army Construction Engineering Research Laboratories.
‡ University of Illinois at UrbanasChampaign.
§ Present address: Department of Chemistry, S. V. University,
Tirupati 517502, India.
| Present address: Environmental Processes Branch, U.S. Army
Construction Engineering Research Laboratories, Champaign, IL
61826-9005.
10.1021/es021013a CCC: $25.00  2003 American Chemical Society
Published on Web 09/05/2003
In recent years biosorption has been recognized as an
effective method of reduction of metal contamination in
surface water and in industrial effluents (1).
Biosorption is defined as the removal of metal or metalloid
species, compounds, and particulates from solution by
biological material (2). Olin et al. (3) and Bailey et al. (4)
conducted an extensive literature search to identify low cost
sorbents with potential for treatment of heavy metal con-
taminated water and waste streams. They identified 12
potential sorbents for lead, cadmium, copper, zinc, and
mercury. Among the sorbents identified, chitosan has the
highest sorption capacity for metal ions (5).
Chitosan is obtained by deacetylation of chitin, which is
extracted from shrimp, crab, some fungi, and other crus-
taceans. Chitosan is not only inexpensive and abundant in
nature, but it also is a good adsorbent for heavy metals.
Chitosan chelates five to six times greater amounts of metals
than chitin. This is attributed to the free amino groups
exposed in chitosan because of deacetylation of chitin (6).
Several investigators have attempted to modify chitosan to
facilitate mass transfer and to expose the active binding sites
to enhance the adsorption capacity. Grafting specific func-
tional groups onto native chitosan backbone allows its
sorption properties to be enhanced (7). Kawamura et al. (8),
Rorrer et al. (9), and Hsein and Rorrer (10) evaluated the
sorption of heavy metals on the porous chitosan beads and
chemically cross-linked beads of chitosan. Chitosan aza-
crown ethers (11, 12), chitosan impregnated with micro-
emulsions (13), and chitosan resins imprinted with metal
ions (14) showed remarkable increase in adsorption capacity
compared to an untreated sample.
Volesky and Holan (1) and Wase and Forster (15) discussed
several biosorbents and their metal binding capacity includ-
ing that for radioactive species such as uranium and thorium.
It has also been recognized that these biosorbents need
further modification and development for commercialization.
Biosorbents, in their natural form, are soft and have a
tendency in aqueous solutions to agglomerate or to form a
gel. In addition, the active binding sites are not readily
available for sorption in their natural form. Transport of the
metal contaminants to the binding sites plays a very
important role in process design. It was also necessary to
provide physical support and increase the accessibility of
the metal binding sites for process applications. Hence, an
attempt was made in the present investigation to prepare a
biosorbent by coating chitosan on alumina.
An alumina supported biosorbent is characterized in this
paper by high-temperature pyrolysis, scanning electron
microscopy, and X-ray photoelectron spectroscopy. The
surface area, pore diameter, and pore diameter distribution
are determined with the nitrogen porosimeter on the basis
of Brunauer-Emmett-Teller (BET) adsorption isotherm.
The objectives of this study were to prepare a composite
chitosan biosorbent, to characterize the sorbent, and to
evaluate the removal of hexavalent chromium from synthetic
as well as field samples. The adsorption capacity of the
biosorbent was evaluated by studying the equilibrium
adsorption isotherms of Cr(VI) in batch and flow modes.
Further, the equilibrium data were fitted to Langmuir and
Freundlich adsorption isotherms, and the values of param-
eters of the isotherms were obtained. Column adsorption
experiments are also performed with a field sample. In
addition, the effect of pH on the extent of adsorption of Cr-
(VI) on the biosorbent was examined. Regenerability of the
composite biosorbent using 0.1 M sodium hydroxide also
was examined.
VOL. 37, NO. 19, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4449
FIGURE 1. Scanning electron micrographs of the composite chitosan biosorbent at (a) 100× and (b) 800× magnification.
Experimental Section
Chemicals. Potassium dichromate, activated alumina, chi-
tosan, and 1,5-diphenylcarbazide were procured from Aldrich
Chemical Co. (Milwaukee, WI). The activated alumina was
Brockman I, standard grade, ∼150 mesh. Potassium chloride
and sodium hydroxide were obtained from Fisher Chemicals
(Fair Lawn, NJ). Potassium sulfate was obtained from EM
Science (Gibbstown, NJ). All salts were ACS certified grade
or better. All solutions were prepared with ASTM type I
deionized water (18 MΩ-H2O grade Barnstead Nanopure).
Preparation of Biosorbent. Composite chitosan biosor-
bent was prepared by coating the ceramic substrate with
chitosan gel as follows. Ceramic alumina 150 mesh was dried
in oven for 4 h at 110 °C. The dried alumina was stirred with
oxalic acid for 4 h at room temperature to coat the surface.
The alumina was filtered from the acid, washed twice with
DI water, and dried in an oven at ∼70 °C under vacuum for
24 h. About 50 g of medium molecular weight chitosan was
slowly added to 1000 mL of 10 wt % oxalic acid solution with
stirring. The acid and chitosan form a viscous mixture (gel),
which must be heated to 40-50 °C to facilitate mixing.
Approximately 500 mL of the chitosan gel was diluted 2-fold
with water and heated to 40-50 °C. About 500 g of the acid-
treated alumina was slowly added to the diluted gel and stirred
for about 36 h. The contents were allowed to settle, and the
clear liquid was filtered out under vacuum with Whatman
41 filter paper. The composite biosorbent was washed twice
with DI water and dried in the oven at 55 °C under vacuum
for 24 h. The coating process was then repeated on the once-
coated biosorbent to increase loading of chitosan on the
alumina. Twenty-four h were used in the second coating
process. Excess oxalic acid in the composite biosorbent was
neutralized by treatment with aqueous NaOH. The mixture
was then filtered with Whatman 41 filter paper, washed with
∼2500 mL of DI water, and filtered. The twice-coated
biosorbent was then dried in the oven under vacuum at 55
°C for about 48 h and transferred to a glass bottle for storage
in a desiccator.
Characterization of the Biosorbent. Characterization of
the composite biosorbent included the following: (a) py-
rolysis, (b) porosimetry, (c) scanning electron microscopy,
and (d) XPS analysis.
(a) Determination of Chitosan Loading on Alumina by
Pyrolysis Technique. The amount of chitosan coated on the
alumina was obtained by measuring the weight loss of
biosorbent from pyrolysis. Dried biosorbent was accurately
weighed into a ceramic boat and placed in a muffle furnace.
The biosorbent was muffled for 6 h at 750 °C. Afterward the
oven was cooled in dry air, and weight loss of the biosorbent
was obtained. Control experiments with empty boat, pure
alumina, acid-treated alumina, pure chitosan, and biosorbent
were also carried out. All the experiments were conducted
in triplicate.
4450 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 19, 2003
(b) Determination of Surface Area and Pore Diameter
by Porosimetry. Surface area, pore volume, and pore
diameter of the composite biosorbent were determined with
a Micromeritics BET instrument by means of adsorption of
ultra purity nitrogen at -196 °C. Average values of these
properties are 125.24 sq.m/g, 0.1775 cm3/g, and 71.125 Å
respectively.
(c) Scanning Electron Microscopy. Surface morphology
was studied with an electron microscope. The scanning
electron micrographs (SEMs) of composite chitosan bio-
sorbent, obtained with an Environmental Scanning Electron
Microscope (XL30-ESEM-FEG, FEI Company, Hillsboro, OR,
U.S.A.), are presented in Figure 1(a),(b).
(d) X-ray Photoelectron Spectroscopy An XPS spectrum
of the composite chitosan biosorbent, obtained on a PHI
model 5400AXIS Ultra Kratos Analytical instrument (Manches-
ter, U.K.), is shown in Figure 2. Figure 3 is an XPS spectrum
of the sorbent after exposure to chromium solution. Figure
3 shows the chromium 2p peaks.
Equilibrium Adsorption Isotherms. Batch equilibrium
adsorption isotherm studies were conducted with aqueous
solutions of Cr(VI) prepared by dissolving appropriate
amounts of potassium dichromate in deionized water. The
concentrations of the prepared metal solutions were verified
using atomic absorption spectroscopy and a UV-Vis spec-
trometer. Equilibrium isotherm studies were conducted at
25 ( 0.5 °C with the mass of composite biosorbent varied
from 100 to 500 mg. Chromium solutions (50 mL) at pH 4.0
were allowed to equilibrate with the composite biosorbent
for 24 h in an oscillating water bath agitated at 200 rpm. After
equilibration, the biosorbent was filtered from the solution
(Whatman 41 filter paper), and the filtrate was analyzed for
metals.
The amount of the metal adsorbed (mg) per unit mass of
biosorbent, qe, was obtained by using the equation
(Ci - Ce)V
qe ) (1)
M
where Ci and Ce are initial and equilibrium concentrations
in mg/L, M is the dry mass of biosorbent in grams, and V is
volume of solution in liters. Equilibrium adsorption experi-
ments were conducted at various pHs to evaluate the pH
profile of the adsorption process. The effect of competing
anions, namely sulfate and chloride, on the adsorption of
Cr(VI) was also evaluated. Sulfate and chloride concentrations
were maintained at 1 millimolar levels in the experiments.
Column Adsorption Experiments. Dynamic flow ad-
sorption experiments were conducted in a glass column of
dimensions about 1 cm internal diameter by 30 cm length.
The bed volume of the column was 30 cm3. The column was
fully jacketed allowing experiments to be carried out at
constant temperature of 25 ( 0.5 °C using a circulating water
FIGURE 2. Composite chitosan biosorbent-survey.
FIGURE 3. Chromium loaded composite chitosan biosorbent.
bath, a Neslab Thermostat, and a Masterflex Pump. Column
ends were fitted with polyethylene filter disks of 100 µm pore
size to retain the composite material. Columns were shaken
while being packed with dried adsorbent to minimize void
volumes and air gaps. Concentrations of column effluents
obtained at various intervals were monitored spectropho-
tometrically after making appropriate dilutions. After the
column was saturated with chromium, it was drained of
remaining aqueous solution by pumping air prior to regen-
eration with 0.1 M sodium hydroxide solution. Samples at
5, 10, 20, and 30 min intervals from the start of the desorption
process were collected for analysis. After regeneration, the
column was washed with DI water before use in subsequent
adsorption runs.
Analytical Procedure. Hexavalent chromium was deter-
mined colorimetrically (16) by measurement of the intense
red-violet complex formed by reaction of chromium(VI) with
1,5-diphenylcarbazide in an acidic medium. A Cary 3E UV-
visible spectrophotometer was used to obtain measurements
of the chromophore complex at its absorbance maximum of
540 nm. Standard stock solutions prepared from potassium
dichromate were used to calibrate the instrument for
hexavalent chromium. The pH of adsorption isotherm
samples was adjusted to 1.0 ( 0.3 with 0.2 N sulfuric acid for
color development. Isotherm sample concentrations were
determined from an absorbance versus concentration cali-
bration curve constructed from standard Cr(VI) solutions. A
precision study revealed that the analytical procedure is
reproducible to better than 1 mg/L.
Results and Discussion
The coating process yielded a stable, granular composite
biosorbent that was wheatish in color.
VOL. 37, NO. 19, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4451
FIGURE 4. Equilibrium adsorption of chromium(VI) on composite
chitosan biosorbent.
SCHEME 1
Characterization of Biosorbent. The average amounts
of oxalic acid and of chitosan coated on to 150-mesh alumina
were obtained by the high-temperature pyrolysis method
described earlier. The results show pure alumina lost about
2.1 wt %. Alumina treated with oxalic acid lost a net weight
of 4.5% and a single coating of chitosan on alumina lost 7.8
net wt %. The net amount of chitosan on the twice-coated
biosorbent was 21.1 wt %. Pure chitosan leaves a residue of
about 0.7 wt % after pyrolysis at 750 °C. Chitin is obtained
from crab shells by acid-base extraction. And chitosan is
obtained from chitin by a deacetylation process. The residue
may be due to a small amount of calcium carbonate that
remains bound with the chitin. Since the residue is such a
small amount, no attempt was made to correct the chitosan
net weight for this.
Oxalic acid is a dicarboxylate used to form a bridge
between alumina and chitosan. As illustrated in in Scheme
1, one carboxylate group forms a relatively strong surface
chelate via ester linkage with the alumina (17) while the other
one forms ionic (or electrostatic) bonds with -NH3+ groups
present in chitosan. The oxalic acid could also form hydrogen
bonds with -OH, -CH2OH, or -NH2 groups on the biopoly-
mer.Scanning electron micrographs (SEMs) of chitosan
coated alumina in Figure 1a,b illustrates that the average
size of particles is 100-150 microns and that the shape of
the composite particle can be described as spherical. Some
particles are agglomerated clusters of the individual particles.
The micropore area of the biosorbent is only 3.3 m2/g
compared to the total surface area (105.2 m2/g). This indicates
that the sorbent is relatively nonporous.
The XPS spectrum provided in Figure 2 reveals carbon,
oxygen, nitrogen, and aluminum are the predominant
elements observed on the surface from binding energies at
289 eV (C 1s), 535 eV (O 1s), 402 eV (N 1s), and 78 eV (Al 2p).
Based upon binding energies, surface moieties of the
composite biosorbent are identified as -CH2OH, -CO, and
-NH2. Chromium is observed in the spectra after exposure
to chromium solution (Figure 3). Figure 3 reveals that the
chromium is partially reduced (∼67%) to chromium(III).
These results are consistent with the observations of Dambies
et al. (35).
4452 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 19, 2003
FIGURE 5. Effect of pH on the adsorption of chromium(VI) on
composite chitosan biosorbent at an initial concentration of 100
mg/L of Cr(VI).
FIGURE 6. Effect of anions on the adsorption of chromium(VI) on
composite chitosan biosorbent.
Equilibrium Isotherms. Results of the equilibrium ad-
sorption isotherm for Cr(VI) at 25 °C and pH 4 are shown in
Figure 4. The isotherm indicates that adsorption increases
with an increasing equilibrium concentration of the sorbate.
The sorption capacity of the composite biosorbent was found
to be 153.8 mg Cr(VI)/g of chitosan. Maximum values of
Cr(VI) adsorbed per unit mass of adsorbent reported in the
literature are 27 mg for chitosan (5), 51 mg for Ni2+ imprinted
chitosan resin (14), and 78 mg and 50 mg for cross-linked
and non-cross-linked chitosan (18). The value reported here
on the twice-coated biosorbent is considerably greater than
that reported elsewhere (5) indicating that the chitosan in
the composite biosorbent has greater adsorption capacity
than unsupported chitosan and the coating process improved
adsorption capacity of chitosan. This improvement may be
attributed to increased surface area and facilitation of
transport of chromium ions to the binding sites on chito-
san.The effect of pH on the adsorption of Cr(VI) on the
biosorbent is shown in Figure 5. Adsorption is greater at low
pH and decreases with increasing pH. Similar behavior was
observed by de Dantas et al. (13) and Schmuhl et al. (18).
Cr(VI) can exist in several stable forms such as Cr2O72-,
HCr2O7-, HCrO4-, and CrO42-, and the relative abundance
of a particular complex depends on the concentration of the
chromium ion and the pH of the solution (28). At lower pH
the sorbent is positively charged due to the protonation of
amino groups, while the sorbate, dichromate ion, exists
mostly as an anion leading to the electrostatic attraction
between sorbent and sorbate. This results in increased
adsorption at low pH. As pH of the solution increases the
sorbent undergoes deprotonation and the adsorption capac-
TABLE 1. Adsorption Capacities of Different Adsorbents for Chromium(VI)
maximum adsorption maximum initial
adsorbent capacity (mg/g) pH concn (mg/L) ref
activated carbon (Filtrosorb 400) 125.5 6.0 260.0 19
sawdust 3.3 6.0 50.0 20
coconut shell activated carbon 20.0 2.5 21
activated carbon (Filtrosorb 400) 145.0 2.5 1000.0 22
sphagnum moss peat 119.0 1.5 1000.0 22
compost 101.0 1.5 1000.0 22
leaf mould 43.0 2.0 1000.0 22
sawdust 39.7 2.0 1000.0 23
sugar beat pulp 17.2 2.0 500.0 23
maize cob 13.8 1.5 300.0 23
sugar cane bagasse 13.4 2.0 500.0 23
coconut husk fibers 29.0 2.1 24
palm pressed-fibers 15.0 2.0 24
pinus sylvestris bark activated by 0.05 N NaCl 19.5 4.5 20.0 25
leather based activated carbon 241.0 3.0 1000.0 26
chitosan 78.0 5.0 1000.0 26
chitosan 27.2 ? ? 5
cross-linked chitosan 50.0 5.0 1000.0 18
metal ion imprinted chitosan 51.0 5.5 1000.0 14
chitosan cross-linked with epichlorohydrin 52.3 5.5 1000.0 14
metal ion imprinted chitosan cross-linked with epichlorohydrin 51.0 5.5 1000.0 14
chitosan cross-linked with ethylene glycol diglycidyl ether 56.8 5.5 1000.0 14
chitosan cross-linked with epichlorohydrin 11.3 3.0 100.0 27
composite chitosan biosorbent 153.8a 4.0 5000.0 present study
a Based on the amount of chitosan (21.1 wt %) on the composite biosorbent. This corresponds to a maximum capacity of 35.4 mg/g of composite

biosorbent.

SCHEME 2

ity decreases. Above this pH, only the adsorption process
influences the removal of Cr(VI) from aqueous medium (22).
In view of this, all experimental data were collected at pH
4.0.
The effects of sulfate, chloride, and both sulfate and
chloride on the biosorption of the Cr(VI) are shown in Figure
6. Anions slightly inhibited the adsorption of Cr2O72- on the
composite biosorbent. The inhibition on adsorption by
monovalent Cl- is less than that of divalent SO42-, as can be
expected. Inhibition effects of both chloride and sulfate do
not appear to be additive. In general, similar reductions in
adsorptions due to anion competition for surface binding
sites have been reported elsewhere in the literature (29-32).
Gao et al. (33) reported that chitosan adsorbs some metals
quantitatively as oxyanions or anionic chloro complexes in
sample solutions by an ion-exchange mechanism. This
implies that the interaction occurs between NH3+ functional
groups in chitosan and Cr2O72- and that the interaction is
chiefly electrostatic attraction in nature. Fu et al. (34)
confirmed an electrostatic attraction by IR and UV spectral
studies. XPS studies (35), which provide identification of the
sorption sites involved as well as the forms of species sorbed,
found that sorption of Cr(VI) does indeed occur on amine
functional groups of the biopolymer as shown in Scheme 2

VOL. 37, NO. 19, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4453
FIGURE 7. Experimental breakthrough curves for adsorption of chromium(VI) from aqueous solution on composite chitosan biosorbent.
Bed volume ) 30 mL, pH ) 4.0, flow rate ) 2.4 mL/min.
FIGURE 8. Regeneration of composite chitosan biosorbent loaded
with chromium(VI) using 0.1 M NaOH. Bed volume ) 30 mL, flow
rate ) 2.6 mL/min.
FIGURE 9. Experimental breakthrough curves for adsorption of
chromium(VI) from field sample on composite chitosan biosorbent.
Bed volume ) 30 mL, pH ) 4.0, flow rate ) 2 mL/min.
(34). Though the ionic (or electrostatic) attraction between
the sorbent and sorbate is the dominate mechanism, other
mechanisms at low and high pH could be responsible for
adsorption. For example at low and high pH, hydrogen
bonding of the metal sorbate (M) or hydroxylated sorbate to
hydroxyl and carboxyl groups of chitosan could occur. Other
forms of chromium exist at both low and high pH and these
4454 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 19, 2003
FIGURE 10. Regeneration of composite chitosan biosorbent loaded
with chromium(VI) from field sample using 0.1 M NaOH. Bed volume
) 30 mL, flow rate ) 2.5 mL/min.
FIGURE 11. Experimental breakthrough curve for adsorption of
chromium(VI) from field samples on composite chitosan biosorbent.
Bed volume ) 30 mL, pH ) 1.99, flow rate ) 2.0 mL/min.
forms should contribute to the overall pH adsorption profile.
Thus the total uptake of Cr(VI) by the composite chitosan
biosorbent is due to (i) ionic attraction, (ii) hydrogen bonding,
and (iii) and weak van der Waals forces.
Langmuir and Freundlich Models. Langmuir and Fre-
undlich models are the simplest and most commonly used
isotherms to represent adsorption of components from a

FIGURE 12. Regeneration of composite chitosan biosorbent loaded
with chromium(VI) from field sample (Co ) 1253 ppm) using 0.1 M
NaOH. Bed volume ) 30 mL, flow rate ) 2 mL/min.
liquid phase on to a solid phase (36). The Langmuir model
assumes monolayer adsorption while the Freundlich model
is empirical in nature. The data are analyzed to obtain
Freundlich and Langmuir parameters. The mathematical
expression of the Langmuir model is
Q0bCe
qe ) (2)
(1 + bCe)
where Ce is the equilibrium concentration of sorbent in
solution (mg/L), qe is the equilibrium loading of sorbate on
sorbant (mg/g), Q0 is the ultimate adsorption capacity (mg/
g), and b is the relative energy of adsorption (L/mg). The
Langmuir model can be linearized to obtain the parameters
Q0 and b from experimental data on equilibrium concentra-
tions and adsorbent loading. A linear plot of Ce/qe verses Ce
was observed and illustrates that adsorption of Cr(VI) on the
composite chitosan biosorbent follows the Langmuir model.
The values of Q0 and b, obtained from experimental data, are
153.85 mg/g and 0.0023 L/mg, respectively, with an R2 value
of 0.9896. The Freundlich model is expressed as
qe ) kCe1/n (3)
where k and 1/n are Freundlich isotherm constants. The
constants obtained from the model and are 0.9565 and 1.4047,
respectively, with an R2 value of 0.9972.
Column Adsorption Studies. Experimental breakthrough
curves for Cr(VI) adsorption from synthetic effluents on the
biosorbent (first two cycles, I and II) at pH 4.0 and 25 °C are
shown in Figure 7. As evident from the figure, no leakage of
Cr(VI) occurs up to 40 bed volumes with an initial influent
concentration (Ci) of approximately 100 mg/L. After 40 bed
volumes, the column effluent concentration (Co) increases
gradually and attains the influent concentration at around
200 bed volumes. The relatively slow increase of effluent to
influent concentration with bed volumes indicates slower
kinetics of adsorption. When the biosorbent is fully loaded
with chromium, pumping air drains the solution in the
column.
The column is regenerated with 0.1 M sodium hydroxide
flowing at 2.6 mL/min. The desorption curve is shown as
cycle I in Figure 8. Maximum desorption occurs within 5 bed
volumes and complete regeneration occurs within 20 bed
volumes with 0.1 M sodium hydroxide. The regenerated bed
is used for subsequent adsorption of chromium, and the
breakthrough curve is shown in Figure 7 as cycle II. A
comparison of the breakthrough curves of cycle I and cycle
II indicates that there is no apparent reduction in the
adsorption capacity of the biosorbent for Cr(VI) from
synthetic effluents. Desorption of Cr(VI) from chitosan is
believed to be mainly due to deprotonation of chitosan amine
groups above pH 10. The adsorption breakthrough curves
for Cr(VI) from wastewater of a chromium plating facility are
illustrated in Figure 9. The wastewater from the chrome
plating facility also contained iron (13 mg/L), cadmium
(0.0065 mg/L), lead (48 mg/L), sulfate (69 mg/L), nitrate (11
mg/L), fluoride (0.32 mg/L), and phosphate (17 mg/L).
To compare with the results of the synthetic effluents, the
wastewater was first diluted to about 100 ppm of Cr(VI) and
adjusted to pH 4.0. As above, cycles I and II represent the
adsorption on virgin biosorbent and regenerated biosorbent.
Desorption curves for diluted field samples are shown in
Figure 10. In the case of field samples the adsorption capacity
of regenerated adsorbent is reduced to some extent in the
second cycle. Breakthrough and desorption curves for an
undiluted field sample (Ci ) 1253 ppm) at a pH 2.0 are
provided in Figures11 and 12, respectively. No chromium is
found in the column effluent (Co) up to 15 bed volumes, and
then the concentration increases very slowly to the initial
influent concentration at around 45 bed volumes. Maximum
desorption occurs within 3 bed volumes. The biosorbent
exhibits greater adsorption capacity due to higher initial
concentration and lower pH.
To summarize, the results show that the coating process
has improved adsorption capacity of chitosan for hexavalent
chromium and suggests that more active sites are exposed
on the composite biosorbent. Column adsorption-desorp-
tion studies indicate that the newly developed composite
chitosan biosorbent could be used to remove chromium(VI)
from industrial effluents.
Acknowledgments
The authors would like to acknowledge analytical support
(X-ray Photoelectron Spectroscopy) received from Dr. Richard
Haas and the Center for Microanalysis of Materials, University
of Illinois, which is partially supported by the U.S. Department
of Energy under Grant DEFG02-91-ER45439. The authors
also thank Mr. Scott J. Robinson, Imaging Technology Group,
Beckman Institute for Advanced Science and Technology,
University of Illinois for help with the scanning electron
micrographs.
Literature Cited
(1) Volesky, B.; Holan, Z. R. Biotechnol. Prog. 1995, 11, 235-250.
(2) Gadd, G. M. Chem. Ind. 1990, 13, 421-426.
(3) Olin, T. J.; Rosado, J. M.; Bailey, S. E.; Bricka, R. M. Report SERDP
96-387 prepared for USEPA and SERDP; 1996.
(4) Bailey, S. E.; Olin, T. J.; Bricka, R. M.; Adrian, D. D. Water Resour.
1999, 33, 2469.
(5) Masri, M. S.; Reuter, F. W.; Friedman, M. J. Appl. Polym. Sci.
1974, 18, 675.
(6) Yang, T. C.; Zall, R. R. Ind. Eng. Chem. Prod. Res. Dev. 1984, 23,
168.
(7) Guibal, E.; Milot, C.; Roussy, J. Water Environ. Res. 1999, 71, 10.
(8) Kawamura, Y.; Mitsuhashi, M.; Tanibe, H.; Yoshida, H. Ind. Eng.
Chem. Res. 1993, 32, 386.
(9) Rorrer, G. L.; Hsein, T.-Y.; Way, J. D. Ind. Eng. Chem. Res. 1993,
32, 2170.
(10) Hsein, T.-Y.; Rorrer, G. L. Sep. Sci. Technol. 1995, 30, 2455.
(11) Yang, Zhikuan; Yuan, Yang. J. Appl. Polym. Sci. 2001, 82, 1838.
(12) Tan, Shuying; Wang, Yuting; Peng, Changhong; Tang, Yurong.
J. Appl. Polym. Sci. 1999, 71, 2069.
(13) de Dantas, T. N.; Dantas Neto, A. A.; de Moura, M. C. P.; Barros
Neto, E. L.; de Telemaco, E. Langmuir 2001, 17, 4256.
(14) Tan Tianwei; He, Xiaojing; Du Weixia. J. Chem. Technol. Biotech.
2001, 76, 191.
(15) Wase, D. A. J,; Forster, C. F.; Ho, Y. S. Low-cost Biosorbent: Batch
Processes in Biosorbents for Metal Ions; Taylor & Francis Ltd.:
London, 1997.
(16) Arnold, E. G.; Lenores, S. C.; Andrew, D. E. Standard Methods
for the Examination of Water and Wastewater; American Public
Health Association: Washington, DC, 1992.
VOL. 37, NO. 19, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4455
(17) Dabson, K. D.; McQuillan, A. J. Spectrochim. Acta, Part A 1999,
55A, 1395.
(18) Schmuhl, R.; Krieg, H. M.; Keizer, K. Water SA 2001, 27, 1.
(19) Huang, C. P.; Wu, M. H. Water Res. 1977, 11, 673.
(20) Srivastava, H. C. P.; Mathur, R. P.; Mehrotra, I. Environ. Technol.
Lett. 1986, 7, 55.
(21) Alaerts, G. J.; Jitjaturant, V.; Kelderman, P. Water Sci. Technol.
1989, 21, 1701.
(22) Sharma, D. C.; Forster, C. F. Bioresour. Technol. 1994, 49, 31.
(23) Sharma, D. C.; Forster, C. F. Bioresour. Technol. 1994, 47, 257.
(24) Tan, W. T.; Ooi, S. T.; Lee, C. K. Envron. Technol. 1993, 14, 277.
(25) Alves, M. M.; Beca, C. G. G.; De Carvalho, R. G.; Castanheira,
J. M.; Sol Pereira, M. C.; Vasconcelos, A. T. Water Res. 1993, 27,
1333.
(26) Manuel, P. C.; Jose, M. M.; Rosa, T. M. 1995, 29, 2174.
(27) Qian, S.; Huang, G.; Jiang, J.; He, F.; Wang, Y. J. Appl. Polym. Sci.,
2000, 77, 3216.
(28) Udaybhaskar, P.; Iyengar, L.; Rao, A. V. S. P. J. Appl. Polym. Sci.
1990, 39, 739.
(29) Kaewsarn, P.; Yu, Q.; Ma, W. Environ. Eng. Sci. 2001, 18, 99.
4456 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 19, 2003
(30) Tobin, J. M.; Cooper, D. G.; Neufeild, R. J. Biotechnol. Bioeng.
1987, 30, 882.
(31) de-Carvalho, R. P.; Chong, K. H.; Volesky, B. Biotechnol. Lett.
1994, 16, 875.
(32) Chong, K. H.; Volesky, B., Biotechnol. Bioeng. 1995, 47, 451.
(33) Gao, Y.; Lee, K.-H.; Oshima, M.; Motomizu, S. Anal. Sci. 2000,
16, 1303.
(34) Fu, M.; Tang, L.; Zhang, P.; Shen, D. Gongcheng Kexueban 1997,
1, 8.
(35) Dambies, L.; Guimon, C.; Yiacoumi, S.; Guibal, E. Colloids
Surfaces, A: Physicochem. Eng. Aspects 2001, 177, 203.
(36) McKay, G.; Blair, H. S.; Gardner, J. K. J. Appl. Polym. Sci. 1982,
27, 3043.
Received for review November 4, 2002. Revised manuscript
received July 21, 2003. Accepted July 21, 2003.
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