Available online at www.sciencedirect.

com

Bioresource Technology 99 (2008) 1211–1217

Experimental binding of lead to a low cost on biosorbent:

Nopal (Opuntia streptacantha)
Patricia Miretzky *, Carolina Muñoz, Alejandro Carrillo-Chávez
Centro de Geociencias-UNAM, Campus Juriquilla, Juriquilla s/n, 76230 Queretaro, Mexico

Received 19 October 2006; received in revised form 13 February 2007; accepted 13 February 2007
Available online 9 May 2007

Abstract

The use of nopal cladodes (Opuntia streptacantha) as raw material for Pb2+ biosorption was investigated. Batch experiments were
carried out to determine Pb2+ sorption capacity and the efficiency of the sorption process under different pH, initial Pb2+ and nopal bio-
mass concentrations. The experimental data showed a good fit to Langmuir and Freundlich isotherms models. The maximum adsorption
capacity for Pb2+ was 0.14 mmol g1 with an efficiency higher than 94% (pH 5.0 and 2.5 g L1 nopal biomass). The Pb2+ kinetics were
best described by the pseudo-second-order rate model. The rate constant, the initial sorption rate and the equilibrium sorption capacity
were determined. The practical implication of this study is the development of an effective and economic technology in which the nopal
biomass did not undergo any chemical or physical pretreatment, which added to nopal abundance in Mexico and its low cost makes it a
good option for Pb2+ removal from contaminated waters.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Nopal; Adsorption; Isotherms; Pseudo-second-order rate; Lead

1. Introduction for treatment of contaminated waters. Due to their low

The use of low-cost adsorbents as a replacement for
costly methods of removing heavy metals from solution
has increased during the last years. Common materials
used are fly ash, zeolite, peat, chitosan, waste slurry, lignin,
seaweed, etc (Bailey et al., 1999; Babel and Kurniawan,
2003).
In this study, we investigated the technical feasibility of
nopal cladodes (Opuntia streptacantha) as a low-cost heavy
metal (Pb2+) adsorbent. In Mexico, fresh weight nopal pro-
duction is about 600,000 tons year1 (Flores, 1997). Fur-
thermore, there are about 3 million ha of wild nopal
(www.sagarpa.gov.mx; www.inegi.gov.mx). Nopal abun-
dance makes it a good low-cost candidate for industrial uti-
lization, principally if it requires little processing. In a
general way, technical applicability and cost-effectiveness
are the key factors when selecting a heavy metal adsorbent
*
Corresponding author. Tel.: +52 442 2381114; fax: +52 442 2381105.
E-mail address: patovior@geociencias.unam.mx (P. Miretzky).
cost, these materials can be disposed without expensive
regeneration, after they have been used.
The cactus cladodes contains, when cut, a polysaccha-
ride mucilage, characteristic of members of the Cactaceae
family (Nobel et al., 1992) that does not gel in the presence
of calcium. The carbohydrate composition of mucilage
from several Opuntia species has been well characterized
(Amin et al., 1970; Trachtenberg and Mayer, 1981; McGar-
vie and Parolis, 1981; Matsuhiro et al., 2006). In general,
the Opuntia sp. cladodes mucilage contains varying propor-
tions of D-galactose, L-arabinose (pyranose and furanose
forms), D-xylose, and L-rhamnose as well as D-galacturonic
acid. Their chemical composition reveals close resemblance
with pectins, structural elements of primary cell walls and
intercellular regions of higher plants. Mucilage content in
dry weight of O. streptacantha has been reported as
2.21% (Goycoolea and Cárdenas, 2003).
Taking advantage of the cladodes properties, nopal muci-
lage is used in culinary applications, as an additive for food
industry, for improving stability and compressibility

0960-8524/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.02.045
1212 P. Miretzky et al. / Bioresource Technology 99 (2008) 1211–1217
of building materials, for cosmetic applications, for improv-
ing house paint as an adhesive for lime, as a flocculant agent
for water purification, and other uses (Sáenz et al., 2004) and
in traditional treatments of diabetes, gastritis, hyperglyce-
mia, etc (Stintzing and Carle, 2005). Nevertheless, there
are very few studies on the use of nopal for heavy metal
removal from aqueous solutions. Barrera-Diaz et al. (2005)
compared the effectiveness of a zeolite and nopal in Cd
and Pb removal from contaminated waters, but they used
the nopal ectodermis, not the entire nopal cladodes.
The aim of the present study is the use of nopal (O.
streptacantha) cladodes biomass as raw material for heavy
metal (Pb2+) biosorption from solution. The mechanism of
Pb uptake from contaminated solutions is investigated
through equilibrium and kinetic experiments under differ-
ent pH, initial metal and nopal biomass concentrations.
2. Methods
2.1. Materials
Nopal plants were collected from Silao (Estado de Guan-
ajuato, México), washed with deionised water to remove
dirt, dried at 60 °C for 24 h, crushed, milled and sieved
through a 0.5 mm sieve (N° 35 mesh). The nopal biomass
cation exchange capacity (CEC) (meq g1) was determined
by titration with 0.1 M NaOH on the nopal acidic form, the
latter being obtained by stirring 10 g L1 of nopal biomass
in an aqueous solution of 0.01 M HCl overnight, then wash-
ing with ultrapure water and drying at 60 °C.
All chemicals used were of analytical-reagent grade.
Ultrapure quality deionised water (Nanopure, Infinity,
Dubuque, Iowa, USA) was used throughout. Pb2+ solu-
tions were prepared by dilution of 1000 mg L1 PE Pure
Standard (Perkin–Elmer, Norwalk, USA). HNO3 and
NaOH (J.T. Baker, Xalostoc, Mexico) solutions (0.01 M)
were prepared by dilution of concentrated acid and base.
All the glassware used for dilution, storage and experi-
ments was cleaned with Extran detergent, thoroughly
rinsed with tap water, soaked overnight in a 20% HNO3
solution and finally rinsed with ultrapure quality water
before use.
2.2. Equilibrium adsorption studies
Batch equilibrium tests were conducted by suspending
the nopal biomass (0.10, 0.20 and 0.30 g) in the Pb2+ metal
solution (40.0 mL) for 120 min in a rotary shaker at
140 rpm. Preliminary experiments of adsorption kinetics
indicated that a period of 120 min was sufficient to attain
equilibrium. At the end of the agitation period, samples
were centrifuged at 3000 rpm for 5 min and then filtered
using 0.45 lm cellulose acetate membrane (Micro Separa-
tions Inc., MSI, Westboro, MA, USA). Different initial
metal concentrations were used (from 0.048 up to
0.241 mM). The experiments were performed at different
pH (3.0, 4.0, 5.0 and 6.0). The initial and final concentra-
tion of Pb2+in the water solution was determined and also
the initial and final pH. Blanks were performed under the
same conditions but in the absence of metals.
The amount of metal adsorbed Qe (mmol g1) was cal-
culated according to
Qe ¼ ðC 0  C e ÞV =W ; ð1Þ
where C0 (mM) is the initial Pb2+ concentration, Ce (mM)
is the equilibrium concentration after the adsorption has
taken place, W is the dried nopal biomass (g) and V the
solution volume (mL).
The efficiency of biosorption (%) was calculated using
% ¼ ðC 0  C e Þ100=C 0 : ð2Þ
2.3. Kinetic studies
The experiments were carried out by suspending nopal
biomass (0.100 g) in 40.0 ml of 0.048, 0.097, 0.145, and
0.245 mM solutions of Pb2+ for 0, 1.0, 7.0, 37.0, 78.0,
120.0 and 184.0 min, as explained before. All the results
obtained in the experiments were corrected from blanks
performed under the same conditions but in the absence
of biosorbents species. All results obtained represent the
average from two replicate experiments.
2.4. Instrumentation
Pb2+, Ca2+ and K+ concentration were determined by
flame atomic absorption spectrophotometry (FAAS) (Per-
kin–Elmer, Aanalyst 300, Shelton, USA) according to stan-
dard methods (American Public Health Association
APHA, 1993). All determinations were performed in tripli-
cate with a relative error <1.0% for all measurements.
3. Results and discussion
3.1. Cation exchange capacity
The estimation of the CEC, that corresponds to the total
number of ionic sites per nopal gram, is essential to the
selection of biosorbents than can be used in the treatment
of metal contaminated waters. The potentiometric titration
of the protonated biomass showed the typical shape attrib-
uted to the carboxylic groups of polygalacturonic acid res-
idues in the mucilage backbone (Fig. 1) with only one
flexion point, corresponding to pKa values ca 3.5. It has
been reported that pectins do not have a well-defined disso-
ciation constant. Apparent pectin pKavalues of 3–4 have
been reported (Deuel and Stutz, 1958). Analysis of the
curve showed that the cation exchange capacity was
0.57 meq g1 of dry nopal, close to the CEC value of the
acid form of sugar-beet pulp (CEC = 0.55 meq g1) (Dron-
net et al., 1997), as pectic substances account for more than
40% of the dry matter of the beet pulp.
 P. Miretzky et al. / Bioresource Technology 99 (2008) 1211–1217 1213

12.0 to 5.0. The lower Pb2+ adsorption at pH 3.0 suggested that

Pb2+ an H+compete for the same adsorption site, as in the
10.0 pH 2.5–5.5, the binding of heavy-metal cations is deter-
mined by the state of dissociation of the weakly acidic
groups (Kratochvil and Volesky, 1998). Pb speciation (V
8.0
MINTEQ, Pb 0.241 mM) showed that Pb2+ was the prin-
cipal specie prior to the adsorption experiments (>97%)
pH

6.0
4.0
2.0
0.0
0.0 3.0 6.0
NaOH 0.1 M (mL)
Fig. 1. Potentiometric titration of acidic form of nopal biomass.
The nopal maximum CEC value was lower than the
CEC values of Potemogeton lucens, Salvinia herzogii and
Eichhornia crassipes macrophytes biomasses CEC = 2.8;
3.1 and 1.6 meq g1, respectively (Schneider and Rubio,
1999), but higher than average capacities for woods: oak
sawdust 0.0982 meq g1, ash shavings 0.0721 meq g1/g,
cedar sawdust 0.0683 meq g1 (Bailey et al., 1999) and
activated carbon prepared from coconut shell: CEC =
0.1605 meq g1 (Sekar et al., 2004).
3.2. Adsorption isotherms
3.2.1. Effect of initial solution pH on metal adsorption
The effect of initial solution pH on Pb2+ removal by the
nopal biomass is shown in Fig. 2. The amount of Pb2+
adsorbed by nopal biomass increased with pH from 3.0
Cº = 0.097 mM Cº = 0.193 mM
0.06
0.05
0.04
Qe mmol g -1
at pH 3.0, 4.0, 5.0 and 6.0. The increase in the amount of
Pb2+ adsorbed with the pH could be explained by the
increase in the density of negative charge on nopal surface
due to ionization of COOH groups present in the nopal
mucilage. Fig. 2 showed a low working pH range for Pb
adsorption compared with conventional weakly acid cation
exchange resins containing the same carboxyl group, prob-
9.0 12.0 15.0 ably due to the pKavalue 3.5 of the polygalacturonic acid.
Further biosorption studies were performed at pH 5.0
because it was the pH in which maximum adsorption was
achieved. The lower Qe values obtained at pH 6 were prob-
ably due to formation of Pb(HO)2 in competition with the
adsorption process.
When performing the adsorption experiments the pH
increased from the initial value of pH 3.0, 4.0 and 5.0 to
3.87, 4.76 and 5.46 (nopal biomass 2.5 g L1, Pb2+ initial
concentration 0.145 mM), respectively at sorption equilib-
rium. Since no Pb2+ precipitation as hydroxide should the-
oretically occur, the increase of pH must have been due to
the binding of H+to the nopal biomass, competing with
Pb2+ ions.
Pb2þ + C5 H9 O5 –COOH $ C5 H9 O5 –COO–Pbþ + Hþ logK a = 3.5
In the blank experiments the increase of pH was always
higher, probably due to H+ exchange with nopal cations in
the carboxyl groups, mainly Ca2+ and K+. These results
constitute an indication of proton displacement by Pb2+
ions.
In order to determine whether ion exchange between
Cº = 0.245 mM
Ca2+ and K+ in the COOH groups of the nopal biomass
and the Pb2+ ions in the solution was substantial, Ca2+
and K+ concentration was measured in the solution bulk,
after the sorption process. When the experiment was per-
formed with a nopal biomass of 2.5 g L1, pH 5.0 and
Pb2+ initial concentration 0.097 mM, the amount of Pb2+
and H+ adsorbed was 0.088 and 0.009 mM, respectively

while the amount of Ca2+ released was 0.92 mM. This

0.03 imbalance between the amount of ions adsorbed and des-
orbed made it difficult to conclude if an exchange process
0.02 was taking place. It is possible that a slight dissolution of
Ca-polygalacturonic nopal biomass was also occurring.
0.01 Similar results on Ca-alginates dissolution were reported
by Chen et al. (1997).
0
The equilibrium adsorption data from the batch experi-
1.0 2.0 3.0 4.0 5.0 6.0 7.0 ments were modeled using Langmuir (Eq. (3)) and Freund-
pH lich (Eq. (4)) adsorption isotherms
2+
Fig. 2. Pb sorption capacity (Qe) at pH 3.0, 4.0, 5.0 and 6.0 (biomass Qe ¼ bQmax C e =ð1 þ bC e Þ ð3Þ
concentration 5 g L1, and initial Pb2+ concentration: 0.097, 0.193 and
0.245 mM). Qe ¼ K F C e1=n ; ð4Þ
1214 P. Miretzky et al. / Bioresource Technology 99 (2008) 1211–1217

where Qmax (mmol g1) is the maximum sorption capacity, 2.5 g L-1 5 g L-1 7.5 g L-1
b (L mmol1) the Langmuir constant related to the binding 0.10
strength, Ce the solution metal ion concentration at equi-
librium (mM) and Qe the metal ion concentration at equi- 0.08
librium in the nopal biomass (mmol g1). KF is the

Freundlich constant or adsorption capacity (mmol g1
(mmol L1)1/n) and n stands for adsorption intensity.
Table 1 shows the isotherm fitting results for Pb2+
adsorption onto nopal biomass at different pH values
and biomass concentrations. Both isotherms fitted experi-
mental sorption data. As expected the sorption capacity
constant KF increased with pH up to pH 5, being lower
at pH 6.0, probably due to Pb(HO)2 precipitation. The
high adsorption affinity of the nopal biomass for Pb was
also reflected in the values of n, the Freundlich constant,
which were in all cases >1 (Table 1).
As expected Langmuir Qmax values for Pb2+ increased
with pH, due to the increase of negative charge on func-
tional groups present on the mucilage. Similar results were
reported by Barrera-Diaz et al. (2005). The amounts of
metal adsorbed under the best experimental conditions
were lower (0.28 meq g1) than the maximum exchange
capacity 0.57 meq g1 obtained by titration of the acid
form of the nopal biomass, but similar to the CEC value
obtained without acid treatment of the nopal biomass
(0.32 meq l1). The b values also increased with pH, being
higher at pH 5.0. Since 1/b represents the equilibrium con-
centration Ce when Qe = Qmax/2, the larger the b value, the
higher the affinity of the nopal biomass with respect to the
metal ions.
The biosorption data fitted the Freundlich and Lang-
muir isotherms, so it could be concluded that the binding
of Pb2+ onto the COOH mucilage functional groups in
the nopal biomass surface was as a monolayer.
3.2.2. Effect of nopal biomass concentration
An increase in biomass concentration generally
increases the amount of adsorbed metal because of an
increase in adsorption surface area (Esposito et al., 2001).
Experimental isotherms for different nopal biomass con-
centrations at pH 5.0 are shown in Fig. 3. Both isotherms
models resulted in a good fit of the experimental data
(Table 1), KF and n values and also Qmax and b values
Qe (mmol g -1)
0.06
0.04
0.02
pH 5.0
0.00
0 0.01 0.02 0.03 0.04 0.05
Ce (m M)
Fig. 3. Isotherms at biomass concentration: 2.5, 5.0 and 7.5 g L1 (pH 5.0,
initial Pb2+ concentration: from 0.048 to 0.245 mM).
resulted in a higher value when a lower nopal biomass con-
centration was used.
Biomass concentration is an important parameter due to
its effect on efficiency (%) and on the amount of metal
adsorbed per unit weight of biosorbent (Qe). Fig. 4a
showed that an increase in the nopal biomass resulted in
a decrease of the Qe (0.055–0.018 mmol g1) with no great
magnitude change in the efficiency (96.6–91.7%) when an
initial Pb2+ concentration of 0.145 mM was used at pH
5.0. The decrease of Qe with increase of biomass concentra-
tion might be due to the formation of aggregates between
the biomass particles at high biomass concentrations,
reducing the effective adsorption area. Similar results were
obtained for Cu biosorption on to the microorganism
Sphaerotilus natans (Esposito et al., 2001) and for Cd on
fungus Aspergillus niger (Barros Junior et al., 2003).
Also the efficiency of metallic biosorption for different
initial Pb2+ concentrations (from 0.048 up to 0.241 mM)
was investigated by carrying out adsorption experiments
at the best experimental conditions: pH 5.0 and biomass
concentration 2.5 g L1. Results (Fig. 4b) showed that
increasing the initial Pb2+ concentration, the Qe increased
1 order, from 0.009 to 0.089 mmol g1, whereas % effi-
ciency decreased only from 99.2 to 93.9. Therefore, nopal
biomass seems to be an efficient material in the Pb2+
removal of contaminated solutions up to 0.241 mM.

Table 1
Fitting parameters for the Freundlich and Langmuir equations
Biomass (g L1) pH Freundlich Qe ¼ K F C e1=n Langmuir Qe = QmaxbCe/(1 + bCe)
KF n r2
Qmax (mmol g1) b (L mmol1) r2
5.0 2 0.055 1.459 0.995 0.026 0.006 0.850
5.0 3 0.239 1.610 0.986 0.054 0.128 0.990
5.0 4 0.357 1.795 0.989 0.061 0.427 0.996
5.0 5 0.442 1.765 0.990 0.064 0.477 0.998
5.0 6 0.349 1.535 0.984 0.059 0.207 0.981

2.5 5 0.960 1.810 0.981 0.140 2.494 0.991

5.0 5 0.442 1.765 0.990 0.064 0.477 0.998
7.5 5 0.286 1.511 0.971 0.038 0.103 0.996
 P. Miretzky et al. / Bioresource Technology 99 (2008) 1211–1217 1215

Qe % significant practical importance ensuring efficiency and

0.06 100.0 economy.
In order to analyze the sorption rates of Pb2+ onto
95.0 nopal biomass, two models were tested, the pseudo-first-
Qe (mmol g -1)

0.04 order model, described by Lagergren, 1898 and the

pseudo-second-order model by Ho and McKay (1999).

%
90.0

0.02 3.3.1. Pseudo-first-order model

pH 5.0 85.0
C0 = 0.145 mM The first-order rate equation of Lagargren is usually
expressed as
0 80.0
2.5 5.0 7.5 log10 ðQe  Qt Þ ¼ log10 Qe  kt=2:303; ð5Þ
biomass (g L-1 ) where Qe is the amount of metal ion adsorbed at equilib-
Qe %
rium by the biomass (mmol g1), Qt is the amount of metal
0.10 100.0 ion adsorbed at any time t (mmol g1) and k is the adsorp-
tion rate constant (min1). Qe (mmol g1) values were
0.08 obtained from the intercept of the plot of Eq. (5) and the
95.0
overall rate constant k (min1) was calculated from
Q (mmol g -1)

0.06 %
the slope. However the Qe values obtained differed from
90.0 the experimental Qe values: 0.018, 0.036, 0.054 and
0.04 0.088 mmol g1 for initial Pb2+ concentration: 0.048,
e

pH 5.0 85.0 0.097, 0.145 and 0.241 mM, respectively. As a consequence,

0.02 biomass 2.5 g L -1 the adsorption reaction could not be considered as pseudo-
first-order even the correlation coefficients were high (Ho
0.00 80.0
0.02 0.05 0.10 0.14 0.19 0.22 0.24
and McKay, 1998).
C0 (mM)
3.3.2. Pseudo-second-order model
Fig. 4. Sorption capacity (Qe) and sorption efficiency (%) (a) for different In the pseudo-second-order model the rate of occupa-
biomass concentrations; (b) for different initial Pb2+ concentrations. tion of adsorption sites is proportional to the square of
the number of unoccupied sites and the number of occu-
pied sites is proportional to the fraction of the metal ion
3.3. Adsorption kinetics
adsorbed. The kinetic rate equation is (Ho and McKay,
1998)
The kinetics experiments were performed using a nopal
biomass of 2.5 g L1, pH 5 and initial Pb2+ concentrations: dQ=dt ¼ kðQe  QÞ ;
2
ð6Þ
0.048, 0.097, 0.145 and 0.241 mM (Fig. 5). The sorption
where k (g mmol1 min1) is the rate of pseudo-second-or-
process was rapid and reached equilibrium in 35 min with
der adsorption and Qe and Q, are the amount of metal ion
an efficiency between 70 and 90%. This rapid kinetic has
adsorbed at equilibrium by the biomass (mmol g1) and
the amount adsorbed at any time t (mmol g1), respec-
tively. The sorption rate v0 ¼ kQ2e (mmol g1 min1) can
0.048 mM 0.097 mM
be regarded as the initial sorption rate as t approaches 0.
0.145 mM 0.241 mM
0.10
Integrating and rearranging Eq. (6)
t=Q ¼ 1=v0 þ t 1=Qe ð7Þ
0.08 pH 5.0
-1
v0 and Qe can be determined by plotting t/Q against t.
biomass 2.5 gL
Results are shown in Table 2. Very good fits were
Qe (mmol g-1)

0.06
observed for all the Pb2+ initial concentrations (r2 values
from 0.999 to 1.000) indicating that the sorption reaction
0.04 followed a pseudo-second-order model. The Qe values
determined from the plot were: 0.019, 0.037, 0.055 and
0.02 0.089 mmol g1 for Pb2+ initial concentration: 0.048,
0.097, 0.145 and 0.241 mM, respectively, in good agree-
0.00 ment with experimental values Qe values (0.018, 0.036,
0 50 100 150 200 0.054 and 0.088 mmol g1). Pseudo-second-order kinetics
t (min)
has been earlier reported for adsorption of Pb2+ on differ-
Fig. 5. Kinetics of Pb2+ adsorption for different initial Pb2+ ent biomasses (Ho and McKay, 1998; Keskinhan et al.,
concentrations. 2003; Bhattacharya and Sharma, 2004).
1216 P. Miretzky et al. / Bioresource Technology 99 (2008) 1211–1217

Table 2
Fitting parameters for the pseudo-second-order and intraparticle diffusion models
C0 (mM) Pseudo-second-order kinetics t/Q = 1/v0 + t 1/Qe Qe experim (mmol g1) Intraparticle diffusion Qt = kdt1/2
v0 (min1 mmol g1) k2 (g mmol1 min1) Qe (mmol g1) r2 kd (mmol g1 min1/2) r2
0.048 0.0110 31.46 0.019 0.999 0.019 0.0002 0.972
0.096 0.0100 7.33 0.037 0.999 0.036 0.0011 0.903
0.145 0.0097 3.27 0.055 1.000 0.054 0.0014 0.992
0.241 0.0096 1.21 0.089 0.999 0.088 0.0030 0.901

As expected the adsorption rate was higher for lower ini-
tial Pb2+ concentration (Table 2). The pseudo-second-order
model is based on the assumption that the rate limiting step
is chemisorption involving sharing or exchange of electrons
between adsorbent and adsorbate. The existence of other
processes such as intraparticle diffusion, mass transfer or
ion interaction is not taken in account. Although experi-
mental data yielded a good fit to this simplified model,
one must bear in mind that the model assumes that all
adsorption sites are homogeneous, and does not consider
the heterogeneous nature of nopal biomass.
If the movement of the solute from the bulk liquid film
surrounding the adsorbent is ignored, the adsorption pro-
cess for porous solids can be explained in 3 steps: (1) mass
transfer (boundary layer diffusion), (2) sorption onto sorp-
tion sites and (3) intra particle diffusion. When the intra-
particle diffusion is the rate-limiting step, the uptake of
the adsorbate varies with the square root of time (Ho
et al., 2000)
Qt ¼ k d t1=2 ;
where kd is the internal diffusion coefficient (mmol g1
min1/2), Qt the amount of metal adsorbed at time t
(mmol g1) and t (min) the sorption time. Experimental
data were fitted to this model. Although the correlation
coefficients were high, the straight lines obtained when fit-
ting experimental data did not pass through the origin
0.048 mM
0.145 mM
0.10
0.08
Q e (mmol g-1)
(Fig. 6), indicating that pore diffusion was not the only
controlling step. The correlation coefficients for the pseu-
do-second-order kinetic model were higher than those for
the intraparticle diffusion model (Table 2), suggesting a
chemical reaction mechanism (Ho and McKay, 2003). This
would indicate that the sorption of Pb2+ is a complex mix
of surface adsorption occurring in the boundary layer of
the nopal particle and intraparticle diffusion. Similar re-
sults were reported by Singh et al. (2006) on Pb removal
by waste maize bran.
4. Conclusions
In this paper, the technical feasibility of nopal, a very
low cost biosorbent for Pb2+ removal from contaminated
water was investigated. Pb2+ biosorption was dependent
on initial pH, initial Pb2+ and nopal biomass concentra-
tions. Sorption capacity was 0.140 mmol g1 (28.9 mg g1)
at pH 5 and nopal biomass 2.5 g L1. In comparison with
ð8Þ adsorbents that stand out for Pb2+ high adsorption capac-
ities (zeolite 175 mg g1), waste slurry 1030 mg g1, lignin
1865 mg g1, chitosan 796 mg g1, seaweed 344 mg g1
(Bailey et al., 1999; Babel and Kurniawan, 2003), nopal
biomass seems to be less efficient, but can be compared
with sphagnum moss peat 30.7 mg g1, groundnut husks
39.3 mg g1, sago waste 46.6 mg g1, coconut shell
26.51 mg g1, activated carbon 2.95 mg g1, pinus pinaster
bark 3.33 mg g1, xhantate 18 mg g1, clay 58 mg g1
(Quek et al., 1998; Bailey et al., 1999).
0.096 mM
The equilibrium sorption data fitted both the Langmuir
0.241 mM
and Freundlich isotherms with high correlation coeffi-
cients, suggesting that the adsorption process followed a
monolayer sorption. Nopal biomass resulted in the efficient
Pb2+ removal (>90%) from contaminated solutions up to
0.241 mM. The kinetics of adsorption was rapid, showing
that 86.5% of biosorption capacity was achieved in the first

0.06 7 min of contact (biomass concentration 2.5 g L1, pH 5.0

and Pb2+ 0.048 mM). The best correlation for the kinetic of
0.04 sorption of Pb2+ onto nopal biomass under the experimen-
tal conditions investigated was provided by the second-
order chemical reaction kinetics, although intraparticle
0.02
diffusion could not be ignored.

0.00 Acknowledgements
0 5 10 15
1/2
t (min1/2)
Financial support of this study was provided by
Fig. 6. Fitting internal diffusion model. UNAM-PAPIIT IN-114102-3 and SEMARNAT-CONA-
 P. Miretzky et al. / Bioresource Technology 99 (2008) 1211–1217
CyT 2002 C01-1420 Projects. The authors wish to thank
the assistance of Jorge Servin in the laboratory work.
References
Amin, E., Awad, O., El-Sayed, M., 1970. The mucilage of Opuntia ficus
indica. Carbohyd. Res. 15, 159–161.
APHA, 1993. Standard Methods for the Examination of Water and
Wastewaters. American Public Health Association. Washington
DC,USA, 874 pp.
Babel, S., Kurniawan, T., 2003. Low-cost adsorbents for heavy metals
uptake from contaminated water: a review. J. Hazard. Mater. 28, 219–
243.
Bailey, S., Olin, T., Bricka, M., Adrian, D., 1999. A review of potentially
low-cost sorbents for heavy metals. Water Res. 33, 2469–2479.
Barrera-Diaz, C., Almaraz-Calderón, C., Olguı́n-Gutierrez, M.A.,
Romero-Romo, M., Palomar-Pardavé, M., 2005. Cd (II) and Pb (II)
separation from aqueous solution using clinoptilolite and Opuntia
ectodermis. Environ. Technol. 26, 821–829.
Barros Junior, L., Macedo, G., Duarte, M., Silva, E., Lobato, A., 2003.
Biosorption of cadmium using the fungus Aspergillus niger. Braz. J.
Chem. Eng. 20, 229–239.
Bhattacharya, K., Sharma, A., 2004. Adsorption of Pb (II) from aqueous
solution by Azadi racta indica (Neem) leaf powder. J. Hazard. Mater.
113, 97–109.
Chen, J., Tendeyong, F., Yiacoumi, S., 1997. Equilibrium and kinetic
studies of copper ion uptake by calcium alginate. Environ. Sci.
Technol. 31, 1433–1439.
Deuel, H., Stutz, E., 1958. Pectic substances and pectic enzymes. In: Nord,
F.F. (Ed.), Advances in Enzymology. Interscience Publishers Inc.,
New York, p. 354.
Dronnet, V., Renard, C., Axelos, M., Thibault, JF., 1997. Binding of
divalent metal cations by sugar-beet pulp. Carbohyd. Polym. 34, 73–
82.
Esposito, A., Pagnanelli, F., Lodi, A., Solivio, C., Veglio, F., 2001.
Biosorption of heavy metals by Sphaerotitus natans: an equilibrium
study at different pH a biomass concentrations. Hydrometallurgy 60,
129–141.
Flores, V., 1997. La producción de nopalitos en México. In Memorias VII
Nacional y V Internacional Congreso sobre conocimiento y aprov-
echamiento del nopal. Monterrey N.L. México. pp. 28–38.
Goycoolea, F., Cárdenas, A., 2003. Pectins from Opuntia spp: a short
review. J. Profess. Assoc. Cactus Develop. 5, 17–29.
1217
Ho, Y., McKay, G., 1998. Sorption of dye from aqueous solution by peat.
Chem. Eng. J. 70, 115–124.
Ho, Y., McKay, G., 1999. Pseudo-second-order model for sorption
process. Process Biochem. 34, 451–465.
Ho, Y., McKay, G., 2003. Sorption of dyes and copper ions onto
biosorbents. Process Biochem. 38, 1047–1061.
Ho, Y., Ng, J., McKay, G., 2000. Kinetics of pollutants sorption by
biosorbents: review. Separ. Purif. Method 29, 189–232.
Keskinhan, O., Goksu, M., Yuceer, A., Basibuyuk, M., Forster, C., 2003.
Heavy metal adsorption characteristics of a submerged aquatic plant
(Myrophyllum spicatum). Process Biochem. 9, 179–183.
Kratochvil, D., Volesky, V., 1998. Advances in the biosorption of heavy
metals. Trends Biotechnol. 16, 291–300.
Lagergren, S., 1898. Zur theorie der sogenannten adsorption geloster
stoffe. Kungliga Svenska Vetenskapsakademiens, Handlingar 24, 1–39.
Matsuhiro, B., Lillo, L., Sáenz, C., Urzúa, C., Zárate, O., 2006. Chemical
characterization of the mucilage from fruits of Opuntia ficus indica.
Carbohyd. Polym. 63, 263–267.
McGarvie, D., Parolis, H., 1981. Methylation analysis of the mucilage of
Opuntia ficus indica. Carbohyd. Res. 88, 305–314.
Nobel, P., Cacelier, J., Andrade, J., 1992. Mucilage in cacti: its aplopastic
capactance, associated solutes, and influence on tissue water relations.
J. Exp. Bot. 43, 641–648.
Quek, S., Wase, D., Forster, C., 1998. The use of sago waste for the
sorption of lead and copper. Water SA 24, 251–256.
Sáenz, C., Sepúlveda, E., Matsuhiro, B., 2004. Opuntia spp mucilage’s: a
functional component with industrial perspectives. J. Arid Environ. 57,
275–290.
Schneider, I., Rubio, J., 1999. Sorption of heavy metals by the nonliving
biomass of freshwater macrophytes. Environ. Sci. Technol 33, 2213–
2217.
Sekar, M., Sakthi, V., Rengaraj, S., 2004. Kinetics and equilibrium
adsorption study of lead (II) onto activated carbon prepared from
coconut shell. J. Colloid Interf. Sci. 279, 307–313.
Singh, K., Talat, M., Hasan, S., 2006. Removal of lead from aqueous
solutions by agricultural waste maize bran. Bioresource Technol. 97,
2124–2130.
Stintzing, F., Carle, R., 2005. Cactus stems (Opuntia spp.): A review on
their chemistry, technology and uses. Mol. Nutr. Food Res. 49, 175–
194.
Trachtenberg, S., Mayer, A., 1981. Composition and properties of
Opuntia ficus indica. Phytochemistry 20, 2665–2668.