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ELSEVIER Bioresource Technology 68 (1999) 95-100

Adsorption of Cd(II) and Pb(II) onto functionalized formic lignin

from sugar cane bagasse
Wilson S. Peternele, Ana A. Winkler-Hechenleitner, Edgardo A. G6mez Pineda*
Departamento de Quimica, Universidade Estadual de Manngtt, Av. Colombo 5790, 87020-090 Maring(z-PR, Brazil

Received 5 September 1997; revised 15 December 1997

Abstract

The effects of temperature, pH and ionic strength on adsorption of Cd(II) and Pb(II) onto carboxymethylated lignin from
sugar cane bagasse have been studied. Adsorption equilibrium data obtained using the batch technique were fitted to the
Langmuir model. A factorial design showed that the most important variables are temperature and ionic strength for the Pb(II)
adsorption in single and binary system respectively. For both metals, maximum binding capacity decreased with the ionic strength
increase. Increasing pH the Pb(II) adsorption is enhanced. Carboxymethylated lignin adsorbed Pb(II) selectively at pH 6.0, 30°C
and 0.1 mol dm -3 of ionic strength. © 1998 Published by Elsevier Science Ltd. All rights reserved.

Keywords: Carboxymethylated lignin; Cadmium; Lead

1. Introduction type of applications. Some chemical modifications can

improve the adsorbent behavior of these materials.
Heavy metals are nowadays among the most Modification reactions include crosslinking and/or
important pollutants in source and treated water, and functionalization to enhance the adsorbent stability
are becoming a severe public health problem. Heavy and/or adsorption capacity. In this way, the low cost
metals removal from aqueous solutions has been tradi- and simplicity of the modification methods are also
tionally carried out by chemical precipitation. However, desirable for applications, for example, in treatment of
metal removal in the precipitation-coagulation system great volumes of industrial and mining wastewater
does not generally allow strict regulatory requirements prior to discharge. Recently, we reported the use of
to be met. In the last few years, adsorption has been lignin from sugar cane bagasse as copper adsorbent
shown to be an economically feasible alternative
method for removing trace metals from wastewater and
water supplies (Huang and Ostovic, 1978; Gabald6n et 0.7 q
al., 1996; L6pez et al., 1995; Allen and Brown, 1995). • • Pb- in binary • Pb-single 1
0.6- • C d - in binary • Cd-single j •
Activated carbon has been the most used adsorbent,
nevertheless it is relatively expensive (Gabald6n et al., o.~
1996; L6pez et al., 1995). In order to obtain cheaper
~. o.4-
adsorbents, lignocellulosics materials have been
0
studied. Agricultural byproducts such as onion skins ~ 0.3- -at

(Kumar and Dara, 1981; Asai et al., 1986), palm kernel IY 0.2-
husk (Omgbu and Iweanya, 1990), peanut skin
0.1
(Randall et al., 1975), modified cellulosic materials
(Shukla and Sakhardande, 1990; Okeimen et al., 1985), 0.0
0.o lo 20 3.0 40 slo
pinus bark (Freer et al., 1989), corn cobs (Hawthorne-
Costa et al., 1995) etc., have received attention in these Ce ( mmol.dm -3 )
Fig. 1. Adsorption isotherms of Pb(lI) and Cd(lI) onto CLSCB at
30°C, pH 6.0 and 0.1 mol dm -3 of ionic strength. Symbols are experi-
*Corresponding author. mental data and solid lines are Langmuir fits.
0960-8524/99/$ - - see front matter © 1998 Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 9 8 ) 0 0 0 8 3 - 2
96 W.S. Peternele et aL/Bioresource Technology 68 (1999) 95-100

(Consolin Filho et al., 1996). The objective of this
study was to contribute in the search for less expensive
adsorbents and utilization possibilities for some
agricultural byproducts, which are in many cases also
pollution sources.
2. Methods
2.1. Lignin extraction
acid and precipitated with cold water, washed with hot
water and dried overnight at 50°C,
2.2. Lignin reticulation
Formic lignin (0.4 g) was dissolved in 10 c m 3 formal-
dehyde (38%) and 5.0cm 3 HCI, then refluxed for
30min. After reflux, lignin was precipitated with
diluted NaOH solution, filtered, washed with water
until neutral pH, and dried at 50°C.

Sugar cane bagasse was extracted sequentially with
n-hexane, ethanol and water in a soxhlet system. The
sample obtained was then air dried. Formic acid
(115 c m 3, 88%) was added to pre-extracted sugar cane
bagasse (10 g) and heated until reflux, when HCI was
added to obtain a 1% solution. After 3 h in reflux, the
sample was filtered and washed with concentrated
formic acid. The solution was concentrated at reduced
pressure until a viscous liquid was formed. This liquid
was poured on cooled water and precipitated lignin
was obtained. This lignin was dissolved in hot formic
2.3. Reaction with chloroacetic acid
To a dispersion of reticulated lignin (2.5g
lignin+20cm 3 of a 10% NaOH aqueous solution),
5 cm 3 of a 36% aqueous chloroacetic acid solution was
added under cooling with tap water. The resulting
solution was kept at 45°C and maintained under
stirring during 4h. After acidification to p H 2 by
diluted sulfuric acid addition, the solid precipitated was
filtered, and washed with water until neutral pH.
2.4. Methodology of adsorption experiments

Adsorption experiments were realized analogously as

described previously (Hawthorne-Costa et al., 1995;
0.4- Consolin Filho et al., 1996). Approx 0.050 g adsorbent
were placed in a 50 c m 3 erlenmeyer and 25.0 c m 3 of
0.3- cadmium and/or lead chloride solutions
(Ci = 1.00 x 10 -3 to 6.00 x 10 -3 m o l d m -3) w e r e a d d e d .
O The dispersions were shaked in a Dubnoff thermostatic
~ 0.2-
bath for 8 h. The dispersions were then filtered and
Clr
metals concentration in solution (Co) were determined
0.1 - • Cd in Binar/
• Pb in Binary through atomic absorption spectrometry using a Varian
• I:~ Spectra AA 10 Plus atomic absorption spectrophoto-
0.0- ~ ~
1 2 3 4 5 6 7 meter, at wavelengths 228.8 nm (for Cd) and 217 nm
Ce (mmol / dm 3) (for Pb) using an acetylene-air flame. The band pass
Fig. 2. Adsorption isotherms of Pb(II) and Cd(II) onto CLSCB at
was 0.5 nm for Cd and 1 nm for Pb. The adsorbed
30°C, pH 5.0, 0.1 mol dm -3 of ionic strength. Symbols are experi- metal concentration (q) was calculated from the differ-
mental data and solid lines are Langmuir fits. ence of the metal remaining in solution and the known

Table 1
Langmuir parameters on Pb(II) and Cd(II) adsorptions onto CLSCB in different conditions (ionic strength: 0.1 mol dm -3)

Metal ion, system, pH 30°C 40°C 50°C

qm (mmol/g) KL (dm3/mol) qm (mmol/g) KL (dm3/mol) q~, (mmol/g) KL (dm3/mol)

Pb(II), single, 6.0 0.519 1.749 0.641 2.058 0.653 1.770

Pb(II), binary, 6.0 0.594 2.146 0.630 2.141 0.635 2.036
Cd(II), single, 6.0 0.338 2.297 0.386 2.030 0.401 2.529
Cd(II), binary, 6.0 0.083 1.671 0.138 2.256 0.187 1.627
Pb(II), single, 5.0 0.388 1.340 0.486 1.197 0.645 0.632
Pb(II), binary, 5.0 0.447 0.708 0.458 0.843 0.552 0.510
Cd(II), single, 5.0 0.602 0.543 0.213 - 0.213 -
Cd(II), binary, 5.0 0.309 0.366 0.101 - 0.096 -
Cd(II), binary, 6.0 0.032 - 0.022 0.075 0.814 0.062
 W.S. Peternele et al./Bioresource Technology 68 (1999) 95-100 97

initial concentration. A digital Micronal B 375 pH equilibrium constant and Ce is metal ion concentration
meter was used for pH measurements and buffer dissolved at the equilibrium) was utilized for estimating
solutions of acetic acid/sodium acetate 0.1 mol dm -3 qm and KL. Single saturation was not observed in some
was used in pH controlled adsorption experiments. isotherms. In these cases, the first saturation step was
considered for qm determination. In general, Pb(II)
adsorption was higher than Cd(II) adsorption. For
3. Results and discussion Cd(II), adsorption was always higher in the single
system compared with the binary system. This behavior
Adsorption of Cd(II) and Pb(II) from chloride salts is expected, considering that in the last case both metal
in aqueous solutions, onto carboxymethylated lignin ions will compete for the disposable binding sites at the
from sugar cane bagasse (CLSCB) was studied in adsorbent surface. However, Pb(II) is more adsorbed
single component and binary systems. Three experi- in the binary than in the single system, which support a
mental parameters were varied: temperature; pH; and synergistic effect. These way, adsorption of Pb(II) is
ionic strength. selective in relation to a binary system (with Cd(II)).
The results obtained at 30°C and at pH 5.0 and 6.0 Adsorption capacity (qm) is enhanced with increasing
are presented as adsorption isotherms in Figs 1 and 2. temperature in all the systems studied here (Table 1).
Saturation of Pb(II) and Cd(II) in both systems and The KL constant shows variable tendencies with
pH isotherms are shown, and could be fitted to a temperature variation. On the other hand, a tendency
Langmuir isotherm (Adamson, 1990). is observed for Pb(II) adsorption: KL at pH 6.0 is
The Langmuir equation, q/qm=KLCJ(I+KLCe) higher for the binary system and KL at pH 5.0 is higher
(where q is the amount of metal ion adsorbed, qm is the for the single system at the three temperatures. In
maximum adsorption capacity, KL is the Langmuir general, adsorption increases when pH is increased.

Q4
0.4-

0,4-
A j f J

03. j~rJ
/. /
0.3-

/
A
0.3-
~ 0.2-
E
E
E 0.2-
o"
01- I~'0.1 . Ionic Strength 1
Ior~c SUeagth

~i
//.m _~ ~ - ~ • •
• 0.1
A 0.5
• 1.0
0.1-

0.0
•
,L
•
0.1
0.5
1.0

GO i i / i B
0.0 1'.0 2.0 4,0 5.0 6.0
0 1 2 3 4 5
Ce( mmol / dm 3) Ce( mmol.dm-3)

"7,
0BiB /
.6
1 "7
0.8--

0.7-
0.6-

,---, 0.5-
O) O,4-
B +

o" Ionic slmnglh

02 oO;, • 6.1
- - A - - 0.5
--=-- 1.0
0 . 0 ~
O.O 0.5 1.0 1.5 2.0 Z5 3.0 3.5 4.0 4.5 O.O 1.0 2.0 3.0 4.0 5.0
Ce(mrnol.dm "3) Ce(mmol.drn-3)
Fig. 3. Adsorption isotherms for Pb(II) in single system on CLSCB at Fig. 4. Adsorption isotherms for Pb(II) in binary system on CLSCB
30oc. Ionic strength is indicated: (A) pH 5.0; (B) pH 6.0. at 30°C. Ionic strength is indicated: (A) pH 5.0; (B) pH 6.0.
98 W.S. Petemele et aL/Bioresource Technology 68 (1999) 95-100

This behavior must be related to the increase in the
ionization degree of the carboxylate groups present in
the modified lignin (Hawthorne-Costa et al., 1995,
Consolin Filho et al., 1996).
NaC1 was added to give ionic strength of 0.5 and
1.0 mol dm -3 to evaluate the ionic strength influence
on the Pb(II) and Cd(II) adsorption experiments at
30°C and at 50°C. Some of these isotherms obtained
are in Figs 3-6. The general tendency was adsorption
decreasing with increasing ionic strength. In many
cases, the addition of the neutral salt resulted in a
change of the shape of the isotherm. These changes
have been interpreted as being due to the presence of
more than one binding site present at the surface lignin
particles (Wieber et al., 1988).
As observed with ionic strength 0.1 mol dm -3, Cd(II)
adsorption was always higher in the single than in the
binary system (Figs 5 and 6). On the other hand, there
is not a definite tendency with respect to pH in Cd(II)
adsorption.
Pb(II) adsorption showed better defined isotherms
(Figs 3 and 4). To qm data, a full 23 factorial design
(three factors, each at two levels) was applied. The
standard experimental matrix for the factorial design
and the results of q , are shown in Table 2. A statistical
analysis was performed on these qm results, and the
main effects and interaction effects for the different
variable combinations were calculated. The results
(Table 2) show that temperature is the most important
factor in the single system (Pb(II)), while ionic strength
is the most important variable for the binary system.
4. Conclusions
Cheap materials such as lignin can be easily modified
in order to obtain new materials able to adsorb heavy
metals ions. Carboxymethylated lignin from sugar cane
bagasse can adsorb Pb(II) and Cd(II) from aqueous
solutions. In general, the Pb(II) adsorption process
obeys Langmuir's model and Cd(II) presents adsorp-
tion in multilayer, especially when the temperature is
higher than 30°C. When ionic strength increases, the
maximum adsorption capacity diminishes.

Iorac Slam~h e ~
• 0.1 . ~
0.2 A ~"g

.---. 0.2.

E
E ~ 0.1,
o"
01, E
. . c _
0.1 ~ • 0.1
- - A - - 0.5
00, - - u - - 1.0

c.(mm /dm3)
010
o.o . ,
1.o .
z0
, , ,
3.0 •
4~o slo 6.0
Ce( mmol.dm"3)

B
0.07
(~5-
°'~ 1 B
A (~D"
OD

"~ Q15- ~ 0.04-

g
O ' Q I o.

(10S' o" o.01°'¢~Z"~ r ' -

(X]D-
0.IX):
o.oo 1.bo zbo abo 4.bo 5.00
Ce (mmol.dm -3)
Fig. 5. Adsorption isotherms for Cd(II) in single system on CLSCB Fig. 6. Adsorption isotherms for Cd(II) in binary system on CLSCB
at 30°C. Ionic strength is indicated: (A) pH 5.0; (B) pH 6.0. at 30°C. Ionic strength is indicated: (A) pH 5.0; (B) pH 6.0.
 W.S. Peternele et al./Bioresource Technology 68 (1999) 95-100 99

Table 2
Adsorption capacity (qm) of CLSCB toward Pb(ll) in different conditions and factorial analysis

Symbol, variable Data (level)

A, ionic strength (mol dm -3) 1.0 ( + ) 0.1 ( - )

B, temperature (°C) 50.0 ( + ) 30.0 ( - )
C, pH 6.0 ( + ) 5.0 ( - )

Variable qm (rnmol/g)

Experiment A B C In single In binary

system system

1 - - - 0.388 0.447
2 + - - 0.141 0.317
3 - + - 0.645 0.552
4 + + - 0.786 0.352
5 - - + 0.519 0.594
6 + - + 0.398 0.425
7 - + + 0.653 0.635
8 + + + 0.505 0.481

Effect in qm For Pb(II) in For Pb(II) in

single system binary system

I 0.504 0.476
A -0.0936 -0.164
B 0.286 0.059
AB 0.090 0.014
C 0.029 0.117
AC - 0.04 1 0.002
BC - 0.165 - 0.011
ABC 0.104 0.021

CMLSCB can adsorb Pb(II) selectively rather than
Cd(II) under special conditions (pH 6.0, 30°C and ionic
strength of 0.1 mol dm-3), when both ions are present
in mixture.
Factorial analysis of Pb(II) adsorption suggests that
temperature is the most important factor in the single
system, adsorption increases with increasing tempera-
ture. When Pb(II) and Cd(II) are present in a binary
system, ionic strength is the most important factor. In
this case adsorption diminishes with increasing ionic
strength.
Acknowledgements
AAWH, EAGP, WSP acknowledge grants from
CNPq Proc. 500.527/95-0 and 300.694/90-3 and
DQI-UEM.
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