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Water Qual. Res. J.

Canada, 2002
Volume 37, No. 2, 379388
Copyright 2002, CAWQ

Cocoa Shells as Adsorbent for


Metal Recovery from Acid Effluent

JEAN F. FISET, RAJESHWAR D. TYAGI AND JEAN-FRANOIS BLAIS*

Institut National de la Recherche Scientifique (INRS-Eau), Universit du Qubec,


2800, rue Einstein, bureau 105, C.P. 7500, Sainte-Foy, Qubec G1V 4C7

Cocoa shells are commonly used in the horticulture field. This inexpensive sub-
strate was studied for metal removal from acidic effluents. Batch adsorption
tests in shake flasks revealed that cocoa shells were particularly efficient for
lead removal. More than 90% of lead could be removed from a mono-metallic
solution containing 51.8 mg Pb/L (250 M Pb) using 20 g/L of cocoa shells.
Langmuir isotherm indicated that cocoa shells have a maximum lead uptake of
7.56 mg/g (36.5 mol/g) at pH = 2.0. Adsorption tests were also successfully com-
pleted with three types of heavily contaminated acid effluents: a multi-element
synthetic solution and effluents produced during sewage sludge and soil
decontamination. These tests have shown that the presence of other metals and
organic matter only slightly decreases the lead removal by cocoa shells. After
adsorption, metals could be eluted using a diluted acid solution (0.5 N) and the
cocoa shells could be reused for many adsorption/desorption cycles.

Key words: cocoa shells, metals, adsorption, lead, metal removal, acid effluent

Introduction
Heavy metals are present in industrial effluents, are non-biodegrad-
able and are a concern for public health. Several approaches have been
studied to reduce the heavy metal content in the effluents, each possess-
ing advantages and disadvantages (Blais et al. 1999; Brooks 1991). The
principal techniques used to reduce metal content are lime precipitation,
membrane filtration, ion exchange, electrolytic methods and adsorption
processes. Each method has shown its limits for industrial application.
The principal constraints are the economical factor because of high capi-
tal and operational costs, and also may be the cost associated with the
generation of secondary wastes which present treatment and disposal
problems (Williams et al. 1998).
Available in large quantities, natural materials are a low-cost alterna-
tive technology for metal removal and for its implementation in the indus-
try. Several workers reported the adsorption of metals by natural products:
peat moss (Couillard 1994), by-products of the forest industry (Fiset et al.
2000), fungi and marine algae (Volesky and Holan 1995) and other low-
cost sorbents (Bailey et al. 1999). Also, other scientists conducted experi-
ments with unconventional adsorption materials such as human hair (Tan
et al. 1985), olive pulp (Gharaibeh 1998), coffee (Macchi et al. 1986), red
mud (Apak et al. 1998) and coconut shells (Arulananthan et al. 1989).

*Corresponding author; blaisjf@inrs-eau.uquebec.ca


380 FISET ET AL.

To date, cocoa shells, a by-product from the cocoa industry, have


never been used as a sorbent for metal removal from acid effluents. Many
processes such as soil and municipal sludge decontamination technologies
produced acid leachate. Metal adsorption at low pH will minimize or
avoid any pH adjustment of the effluent and consequently decrease the
cost of chemical reagents, facilitating its implementation in the industry.
With regard to the problems that the industry has to face, the objective of
this work was to study the adsorption of metals from acid effluents by
cocoa shells. Batch tests have shown that agro-industrial waste is a promis-
ing adsorbent for metal. The adsorption data obtained from a multi-ele-
ment synthetic solution and process effluents were presented and ana-
lyzed as well as lead adsorption from a mono-metallic (lead) solution.

Materials and Methods

Cocoa Shells
Cocoa shells have been obtained from Les Distributions Propep inc.
(Qubec, Canada). The cocoa shells were pre-washed with deionized
water and dried in an oven for 24 h at 50C. Thereafter, they were crushed
and sieved, and the fraction inferior to 2 mm was used for this study.

Acid Effluents
A multi-element synthetic solution (MES) 250 M was made with
the following metal nitrate salts: Al(NO3)3.9H2O, Ca(NO3)2.4H2O,
Cd(NO 3)2.4H2O, Cr(NO3)3.9H2O, Cu(NO3)2.3H2O, Fe(NO3)3.9H2O,
Mg(NO3)2.4H2O, Mn(NO3)2.4H2O, Ni(NO3)2.6H2O, Pb(NO3)2, Zn(NO3)2.
6H2O and NaNO3. Chemical composition of the MES is shown in
Table 1. A single-element solution (SES) containing 250 M Pb(NO3)2
was also used to determine the lead adsorption capacity of cocoa shells.
The salts were dissolved in double deionized water acidified with 2%
(v/v) HNO3. All the reagents were of analytical grade.
Sewage sludge filtrate (SSF) was obtained after decontamination of
Montreal Urban Community sewage sludge (Qubec, Canada) by a chem-
ical leaching process using an inorganic acid and an oxidant agent. The
SSF was centrifuged (18 000 x g) for the removal of solid matter. The SSF
contained 10.30 g/L of total solids, 2.17 g/L of suspended solids, 1.02 g/L
of dissolved organic carbon (DOC) and the pH was 2.45. The chemical
composition of SSF is presented in Table 2.
Contaminated soil filtrate (CSF) was prepared by chemical leaching
of a metal-contaminated soil using hydrochloric acid. After leaching, the
acid leachate was separated by filtration on Whatman No. 4 membranes.
The pH of the CSF was 2.20. The chemical composition of CSF is reported
in Table 3.

Metal Adsorption Study


Adsorption tests using volumes of 200 mL of the different multi-
element effluents (MES, SSF, CSF) were done in 500-mL capacity
METAL ADSORPTION BY COCOA SHELLS 381

Table 1. Metal removal from the multi-element synthetic solution (MES) after
24 h at pH = 2.00 and using 20 g/L of cocoa shells

Initial concentration Final concentration Removal


Element (mg/L) (M) (mg/L) (M) (%)

Al 7.10 263 6.30 234 11.3


Ca 9.30 232 26.9 671 -189
Cd 28.7 255 22.7 202 20.9
Cr 13.1 252 10.1 194 22.9
Cu 16.4 258 11.7 184 28.7
Fe 14.1 252 8.60 154 39.0
Mg 6.10 251 31.9 1310 -423
Mn 13.7 249 11.9 217 13.1
Na 5.50 239 63.4 2760 -1050
Ni 14.9 254 12.1 206 18.8
Pb 54.0 261 4.10 19.8 92.4
Zn 16.9 258 13.5 206 20.1

Erlenmeyer flasks. A concentration of 20 g/L of cocoa shells was used for


these adsorption tests. The pH of the solutions was adjusted at 2.00 with
a sodium hydroxide solution (10 N). All experiments were conducted at
25C and the flasks were agitated at 150 rpm in an orbital shaker. Samples
of 15 mL were collected at the following times: 0, 0.5, 1, 2, 4, 6 and 24 h for

Table 2. Metal removal from the sewage sludge filtrate (SSF) after 24 h at
pH = 2.45 and using 20 g/L of cocoa shells

Initial concentration Final concentration Removal


Element (mg/L) (M) (mg/L) (M) (%)

Al 119 4410 89.5 3320 24.8


Ca 21.5 536 22.9 572 -6.5
Cd 0.27 2.40 0.19 1.69 29.6
Cr 0.97 18.7 0.42 8.08 56.7
Cu 11.3 178 2.61 41.1 76.9
Fe 171 3060 181 3240 -5.8
Mg 35.0 1440 36.6 1510 -4.6
Mn 7.50 137 6.60 120 12.0
Na 121 5270 108 4700 10.7
Ni 0.69 11.8 0.63 10.7 8.7
Pb 0.58 2.80 0.00 0.00 100
Zn 13.7 210 10.2 156 25.5
382 FISET ET AL.

Table 3. Metal removal from the contaminated soil filtrate (CSF) after 24 h at
pH = 2.20 and using 20 g/L of cocoa shells

Initial concentration Final concentration Removal


Element (mg/L) (M) (mg/L) (M) (%)

Al 22.9 849 8.1 300 64.6


Ca 19.7 492 19.9 497 -1.0
Cd 0.20 1.78 0.11 0.98 45.0
Cr 0.10 1.92 0.03 0.58 70.0
Cu 7.50 118 2.09 32.9 72.1
Fe 6.20 111 1.95 34.9 68.5
Mg 42.4 1740 37.3 1540 12.0
Mn 13.7 249 10.2 186 25.5
Na 35.4 1540 28.6 1180 19.2
Ni 0.30 5.11 0.50 8.51 -66.7
Pb 7.50 36.2 0.59 2.85 92.1
Zn 24.9 381 16.7 255 32.9

soluble metal analyses and pH measurements. The samples were filtrated


through Whatman 934-AH membranes and the filtrates were acidified
with concentrated nitric acid. Experiments were carried out in triplicate.

Langmuir Isotherm
The adsorption process is often described in terms of isotherms. They
represent the relationship between the concentration of a species in solution
and the adsorbed quantity at a constant temperature. Isotherms are usual-
ly used to establish the highest metal adsorption capacity for an adsorbent.
Langmuir isotherm is expressed by equation 1 and the corresponding lin-
ear relationship is given by equation 2 (Stumm and Morgan 1996).

q = b Ce qmax/(1 + b Ce) (1)

1/q = 1/qmax + 1/(b qmax Ce) (2)

Where q is the uptake of the solute (weight of lead adsorbed per unit
weight of adsorbent); qmax is the maximum uptake (mg of lead per unit
weight of adsorbent); Ce is the equilibrium concentration (mg/L) of solute
in the solution; and b is a constant related to the energy of adsorption.
Isotherm experiments were carried out in triplicate using 100-mL
aliquots of SES in contact with 0.2, 0.5, 1.0, 1.5, 2.0 and 3.0 g of cocoa
shells in shake flasks. The pH of the solutions was adjusted to 2.0. Each
experiment was conducted at 25C and agitated in an orbital shaker at
150 rpm. Samples of 15 mL were drawn after 24 h followed by filtration
and metal analysis.
METAL ADSORPTION BY COCOA SHELLS 383

Desorption Study
After lead adsorption from the synthetic solution, the cocoa shells
were washed with deionized water to remove any excess of lead solution
on the surface. Thereafter, the cocoa shells have been treated with 50 mL
hydrochloric acid, 0.5 N for 3 h, in an Erlenmeyer flask agitated at
150 rpm. The adsorbent was washed and oven-dried for 24 h at 50C and
was reused in another adsorption cycle. This procedure was repeated for
a total of four adsorption/desorption cycles and conducted in triplicate.

Analytical
The pH of the solutions was monitored by an Orion 420A pH meter.
The metal concentrations in solution were determined by Inductively
Coupled Plasma with Atomic Emission Spectrometry (ICP-AES) (Thermo
Jarrel Ash, Atom Scan 25).

Results and Discussion

Adsorption Study
The time course for adsorption of Cu(II), Fe(III), Ni(II) and Pb(II)
using 20 g/L of cocoa shells is shown in Fig. 1. The Pb(II) concentration in
solution rapidly declined until the equilibrium concentration (20 M) is
reached between the amount of Pb(II) adsorbed and the lead in solution.
The equilibrium time (approximately 1 hour) is essentially the same for

Fig. 1. Time course of metals removal from the multi-element synthetic solution
(MES) at pH = 2.00 using 20 g/L of cocoa shells: ( ) Cu, ( ) Fe, ( ) Ni, ( ) Pb.
384 FISET ET AL.

Cu(II), Fe(III), Ni(II), Pb(II) and also for the other heavy metals present in
the multi-element synthetic solution investigated in this study.

Adsorption Isotherm
During the adsorption process, several metals could be adsorbed on
the surface. Multi-element solution involved the competition between the
metals for the available sites of adsorption. Consequently, metal removal
yield decreased for each metal. To evaluate the effect of the other metals
for lead removal, the Langmuir equation was applied for qualitative rea-
son. Figures 2 and 3 clearly show that the adsorption of lead by cocoa
shells from the SES and the MES is described by a Langmuir isotherm.
Lead maximum uptake (qmax) was 7.56 mg Pb/g of cocoa shells in the SES
at pH = 2.0. The presence of other metals and elements only slightly
decreased the lead adsorption capacity of cocoa shells. In fact, a qmax value
of 6.07 mg Pb/g of cocoa shells was measured using the MES.
To date, no mechanisms or data related to adsorption of lead by
cocoa shells is reported in the literature. The lead adsorption was partic-
ularly studied on oxides of titanium (Stumm et al. 1976), silicon (Davies
and Leckie 1978; Schindler et al. 1976; Stumm et al. 1976), manganese
(Gadde and Laitinen 1973; McKenzie 1980), aluminum (Benjamin and
Leckie 1981; Hohl and Stumm 1976) and iron (Forbes et al. 1976;
McKenzie 1980; Balistrieri and Murray 1982) but not with cocoa shells.
According to many researchers, proteins, carbohydrates and phenolic
compounds are responsible for metal sorption by natural products
through carboxylic, hydroxylic, sulfate, phosphate and amine groups

Fig. 2. Lead sorption isotherm for cocoa shells at pH = 2.00: ( ) single-element


solution (SES), ( ) multi-element synthetic solution (MES).
METAL ADSORPTION BY COCOA SHELLS 385

Fig. 3. Linear Langmuir isotherm for lead adsorption by cocoa shells at pH = 2.00:
( ) single-element solution (SES), ( ) multi-element synthetic solution (MES).

which exist in cellulosic (cellulose, hemicellulose, lignin) materials (Al-


Asheh and Duvnjak 1998).

Metal Adsorption Study


Table 1 shows the initial and final concentrations of all elements in the
MES and the corresponding removal yields. A yield of 92% of lead removal
was observed at pH = 2.0 using 20 g/L of cocoa shells. Lower removal
yields were obtained for Fe, Cu, Zn and Cr as reported in Table 1. The
application of various chemical pre-treatments of cocoa shells as a phos-
phorylation (Guthrie 1952), an acid, or a caustic treatment did not signifi-
cantly increase the adsorption capacities for this sorbent (Fiset 2001).
The removal efficiencies of Pb, Cu and Cr from the SSF were 100, 76
and 57%, respectively (Table 2). Higher metal adsorption efficiency was
due to low metal content in the SSF. Results from the CSF (Table 3)
revealed that cocoa shells removed 93% of lead with an initial concentra-
tion of 7.50 mg/L. Removal yields of 73% and 69% were measured for
copper and iron from the CSF.
Comparing the metal removal of the three leachates, metal removal
efficiency was in the following order: Pb > Fe > Cu > Cr for the MES, Pb >
Cu > Cr > Al for the SSF and Pb > Cu > Fe >Al for the CSF using the CS. In
this study, Ca and Mg ions were released in solution suggesting an ion
exchange mechanism. However, further investigations should be done to
determine the mechanism of adsorption and also the impact of the compe-
tition of the cations and the effect of the anions in the solutions.
Nevertheless, these results showed that lead adsorption was possible in
various types of solution. The adsorption of lead on oxide and oxyhydrox-
386 FISET ET AL.

ide is not relatively affected by the presence of other metal cations in simi-
lar concentrations or by changes of the ionic strength (EPRI 1987). This
trend was also observed in this study because lead percent removal was
over 90% using three different effluents. Furthermore, the majority of the
anions such as ClO4-, Cl- and NO3- have only slight influence on the adsorp-
tion of lead on iron oxides, but ions such as SO42- had increased the adsorp-
tion of lead, possibly due to the reduction of the surface positive charge due
to the adsorption of the sulfate ions (Balistrieri and Murray 1982). The MES,
SSF and CSF have different metal concentrations, dissolved organic matter
and anionic species but cocoa shells performed well in all cases.

Desorption Study
Experiments were also conducted in order to evaluate the possibility
of regenerating the cocoa shells. The tests showed that it was possible to
regenerate the cocoa shells for at least four cycles, without a physical dete-
rioration of this adsorbent and without a decrease of the lead adsorption
performance. As observed in Fig. 4, the adsorption efficiency of several
metals (Al, Cd, Cr, Mn, Ni, and Zn) decreased when the number of cycles
of sorption/desorption increased. However, this trend was not observed
for lead. This phenomenon causes an increase of the selectivity for lead
removal following the regeneration of cocoa shells.

Conclusion
The elimination of metals by vegetal biomass highlights the adsorp-
tion capacity of inexpensive materials for the removal of potentially toxic

Fig. 4. Metal removal efficiencies from the multi-element synthetic solution


(MES) during four consecutive cycles of adsorption/desorption using 20 g/L of
cocoa shells.
METAL ADSORPTION BY COCOA SHELLS 387

metals from effluents. This study has demonstrated that cocoa shells con-
stitute an efficient sorbent for lead removal from different types of very
acidic solutions. Tests have also shown that the presence of other metals
and organic matter only slightly decreases the lead removal by cocoa
shells. Finally, this research has also shown that metals adsorbed can be
eluted using a diluted acid solution and the cocoa shells can be reused for
many adsorption/desorption cycles.

Acknowledgments

Sincere thanks are due to the National Sciences and Engineering


Research Council of Canada (Grant 216819-99) and FCAR (Grants 00-NC-
1961 and 00-ER-2428) for their financial support.

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