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Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 76:593±597 (2001)

DOI: 10.1002/jctb.418

Adsorption of selected toxic metals by modified


peanut shells
Srinath Chamarthy,1 Chung W Seo1* and Wayne E Marshall2
1
Department of Human Environment and Family Sciences, Food and Nutrition Laboratory, North Carolina A&T State University, 1601 E
Market Street, Greensboro, NC 27411, USA
2
United States Department of Agriculture, Agricultural Research Service, Southern Regional Research Center, 1100 Robert E Lee Blvd,
PO Box 19687, New Orleans, LA 70179, USA

Abstract: The objective of this study was to modify peanut shells to enhance their adsorptive properties
toward the metal ions cadmium (Cd2‡), copper (Cu2‡), nickel (Ni2‡), lead (Pb2‡) and zinc (Zn2‡).
Milled peanut shells were initially washed with water or 0.1 N NaOH or left unwashed. Following these
treatments or lack of treatment, the shells were either left unmodi®ed or modi®ed by a heat treatment
in the presence of either 1.0 M phosphoric acid or 0.6 M citric acid. Modi®ed peanut shells were
evaluated either for adsorption ef®ciency or for adsorption capacity using the ®ve metal ions listed
above. Adsorption ef®ciencies and capacities were compared with ef®ciencies and/or capacities for the
commercial chelating or cation exchange resins Amberlite 200, Amberlite IRC-718, Duolite GT-73,
and carboxymethylcellulose. For the adsorption ef®ciencies of individual metal ions, modi®ed peanut
shells met or exceeded the adsorption values for cadmium, copper, nickel or zinc ions compared with
the commercial resins Duolite GT-73 and carboxymethylcellulose. In a solution containing all ®ve
metal ions, modi®ed peanut shells met or exceeded the adsorption ef®ciencies for cadmium, copper
and lead ions compared with Duolite GT-73, Amberlite IRC-718 and carboxymethylcellulose.
Adsorption capacities of modi®ed peanut shells met or exceeded the adsorption capacity of Duolite
GT-73 for lead ions only. Citric or phosphoric acid-modi®ed peanut shells showed a preference for
Cu2‡ and Pb2‡ and appear promising as potentially inexpensive adsorbents for selected metal ions.
# 2001 Society of Chemical Industry

Keywords: peanut shells; citric acid; phosphoric acid; metal ions; adsorbents

1 INTRODUCTION the peanut shells. Azab and Peterson9 and Wartelle


Peanut shells are low density, high volume agricultural and Marshall10 used alkali treatment to increase Cd2‡
waste which, in part, are used in animal feed and Cu2‡ uptake, respectively, by peanut shells.
formulations or are burned for energy. These are low Okieimen et al 11 noted that treatment of peanut shells
value uses for the shells and additional product outlets with the chelating agent EDTA improved subsequent
need to be identi®ed to create higher value products. Cd2‡ and Pb2‡ sorption. Recently, Wafwoyo et al 12
In order to add value to peanut shells, attention has reacted peanut shells in the presence of either
focused on the utilization of peanut shells as adsor- phosphoric acid or citric acid to greatly increase the
bents. In this regard, peanut shells have been modi®ed metal ion binding ability of the shells.
by heat or chemical treatment to improve their ability The present study is a continuation of research
to adsorb different metal ions or organic compounds. reported by Wafwoyo et al. 12 The objective of this
There have been several reports1±7 that have study was to extend the results reported by Wafwoyo et
described peanut shell (hull) activated carbon for al 12 including: (1) adding a ®fth metal ion, namely
adsorption of various metal ions and organic com- Pb2‡, to solutions containing the four metal ions,
pounds. In addition to their use as activated carbons, Cd2‡, Cu2‡, Ni2‡ and Zn2‡, (2) adding the commer-
peanut shells have been used as is or undergone cial cation exchange resin, carboxymethylcellulose, for
different modi®cations to enhance their ability to comparison purposes and (3) determining adsorption
sequester metal ions from solution. Henderson et al 8 capacities for modi®ed peanut shells and commercial
reported that untreated peanut shells adsorbed sig- resins.
ni®cant amounts of Hg2‡, Cu2‡, Ni2‡ and Zn2‡ at low Phosphoric and citric acids were again chosen as
concentrations of the metals. A 1 h exposure of the modifying agents in this study because of the promis-
shells to these metal ion solutions signi®cantly ing metal ion adsorption results achieved by Wafwoyo
increased their adsorption by decreasing the size of et al 12 using these modi®cation strategies.

* Correspondence to: Chung W Seo, Department of Human Environment and Family Sciences, Food and Nutrition Laboratory, North Carolina
A&T State University, 1601 E Market Street, Greensboro, NC 27411, USA
Contract/grant sponsor: USDA-CSREES Capacity Building Program; contract/grant number: 95-38814-1729
(Received 26 October 2000; revised version received 4 January 2001; accepted 13 February 2001)

# 2001 Society of Chemical Industry. J Chem Technol Biotechnol 0268±2575/2001/$30.00 593


S Chamarthy, CW Seo, WE Marshall

2 MATERIALS AND METHODS on a dry weight basis of adsorbent. Adsorption


2.1 Peanut shells capacity was calculated using the Langmuir model,
Peanut shells were a gift from the Carolina±Virginia which in its non-linear form is given as:
Peanut Growers Association (Suffolk, VA). They have
X ˆ ‰Xm  K  Ce Š=‰…1 ‡ K †  Ce Š …1†
a bulk density of 0.22 g cm 3 for a particle size range of
0.85 to 2.00 mm and consist predominantly of Where: X = amount of solute adsorbed per unit weight
cellulose (45.3%).10 Other major components include of adsorbent; Ce = equilibrium concentration of solute;
lignin (32.8%), hemicellulose (8.1%), protein (4.9%) Xm = maximum adsorption capacity of adsorbent for
and ash (2.3%).10 solute and K = adsorption equilibrium constant.
Sodium hydroxide, cupric sulfate, the nitrates of Solving eqn (1) by non-linear, least squares regres-
cadmium, lead, nickel and zinc, citric acid monohy- sion analysis determines values for Xm. These values
drate, acetic acid (glacial), sodium acetate (mono- were obtained by using a regression analysis program
basic), 85% phosphoric acid, and nitric acid (trace in Sigma Plot v 4.0 (SPSS Inc, Chicago, IL). In all
metal grade) were purchased from Fischer Scienti®c cases, regression values (r2) were such that the
(Fair Lawn, NJ). Plasma emission standards for the Langmuir model predicted the data set at p < 0.05.
®ve metal ions were obtained from Solutions Plus Inc The adsorption data obtained were analyzed by a
(Fenton, MO). The commercial resins Amberlite two-way ANOVA followed by Fischer's least signi®-
IRC-718, Amberlite 200, Duolite GT-73, and car- cant difference (LSD) using the SAS system ANOVA
boxymethylcellulose were purchased from Supelco procedure at a = 0.05 (v 6.12 from SAS Institute Inc,
(Bellefonte, PA). Amberlite IRC-718 and Duolite Cary, NC).
GT-73 are chelating resins designed to be selective for
certain metal ions, including Cu2‡, Pb2‡, Cd2‡, and 2.6 Moisture determination
Zn2‡, while Amberlite 200 and carboxymethylcellu- The moisture content of the peanut shells and
lose are general-purpose cation exchange resins. commercial resins were determined as loss of weight
on drying according to AAOC method 24.003 (a).13
2.2 Preparation of peanut shells Moisture values varied from 1.4 to 7.2% for acid-
The preparation of milled peanut shells and treat- modi®ed shells and 7.7 to 59% for commercial resins.
ments for unwashed, base-washed and water-washed
peanut shells were carried out as described by
Wafwoyo et al. 12 Peanut shell modi®cations with 3 RESULTS AND DISCUSSION
0.6 M citric acid or 1.0 M phosphoric acid were also Wafwoyo et al 12 clearly demonstrated that little, if any,
carried out according to the methods of Wafwoyo et metal ion adsorption occurred in the absence of
al. 12 phosphoric acid or citric acid modi®cation of peanut
shells. Shells exposed to no washing, water washing or
2.3 Metal ion solutions base washing alone adsorbed less than 0.2 mmol g 1
The metal ions chosen for the study were Cu2‡, Pb2‡, each of the ®ve metal ions. For some of the samples, no
Cd2‡, Zn2‡, and Ni2‡. All single metal ion and metal ion adsorption was observed. Wafwoyo et al 12
multiple metal ion solutions were made to a concen- also observed little or no metal ion adsorption when
tration of 20 mM in 0.07 M sodium acetate±0.03 M non-modi®ed shells were placed in contact with a
acetic acid buffer, pH 4.8. The multiple metal ions mixture of metal ions Cd2‡, Cu2‡, Ni2‡ and Zn2‡.
contained all ®ve metal ions, each at 20 mM. To Lead ions were not included. On the basis of these
produce adsorption isotherms, single metal ion solu- published results, only acid-modi®ed shells were
tions of all ®ve metals were made to concentrations of evaluated in the present study.
5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 mM in the
sodium acetate±acetic acid buffer, pH 4.8. 3.1 Adsorption of individual metal ions
Phosphoric acid modi®cation of unwashed, water-
2.4 Metal ion adsorption of modified peanut shells washed and base-washed shells gave products that
and commercial resins showed little difference in their ability to sequester
Metal ion adsorption was carried out according to the individual metal ions (Table 1). Therefore, pre-
procedure used by Wafwoyo et al. 12 The pH of the treatment of shells with water or base may not be
solutions was measured at the beginning and end of necessary for phosphoric acid modi®cation to be
the metal ion adsorption experiments and varied effective. However, citic acid modi®cation appears to
between 4.6 and 5.0 for any given experiment. be most effective with base-washed shells. The
reason(s) for this observation is not known. Exposure
2.5 ICP and statistical analysis to base removes more colored material from the shell
ICP analyses were performed on the ®ltrates as than water washing. The removal of colored com-
described by Wafwoyo et al. 12 pounds and the concomitant changes that occur in the
The metal ions remaining in solution after adsorp- shell apparently enhance citric acid but not phosphoric
tion (equilibrium concentration) and the amount acid modi®cation. Additionally, treatment with NaOH
adsorbed (mmol) per g of sample were determined may saponify and remove surface lipids from the

594 J Chem Technol Biotechnol 76:593±597 (2001)


Adsorption of toxic metals by modi®ed peanut shells

Metal ion
Adsorbent Cd 2‡ Cu 2‡ Pb 2‡ Ni 2‡ Zn 2‡
Unwashed ± citric acid 0.31e 0.58d 0.35h 0.27e 0.31f
Unwashed ± phosphoric acid 0.50cd 0.66c 0.77e 0.33d 0.46d
Water-washed ± citric acid 0.33e 0.56d 0.37h 0.27e 0.26g
Water-washed ± phosphoric acid 0.41e 0.72c 0.80e 0.37c 0.47d
Base-washed ± citric acid 0.34e 0.68c 0.48g 0.41c 0.40e
Base-washed ±phosphoric acid 0.43de 0.69c 0.66f 0.30de 0.47d
Duolite GT-73 0.49d 0.70c 1.15d 0.37c 0.54c
Amberlite IRC-718 1.80a 2.19a 2.30a 0.60b 2.03a
Amberlite 200 1.27b 0.98b 1.84b 1.18a 1.30b
Carboxymethylcellulose 0.61c 0.70c 1.53c 0.27e 0.34f
a
Values (mmoles g 1 dry wt) in the same column with a common subscript are not signi®cantly
Table 1. Adsorption efficienciesa of individual metal different at a = 0.05. Values are means of duplicate determinations where the standard error was
ions by modified peanut shells and commercial <5.0%.
resins Values in boldface represent shell adsorption that meets or exceeds resin adsorption.

peanut shells, thus exposing more sites for the inter- washed, citric acid-modi®ed shells performed slightly
action between citric acid and components (cellulose better at metal ion adsorption than either unwashed or
and hemicellulose) of the shell. In the case of phos- water-washed shells. For phosphoric acid modi®-
phoric acid, exposure to the acid may, to a limited cation, wash type had little effect on metal ion
degree, hydrolyze lipid and remove some surface lipid adsorption. These results are similar to the results
in a manner similar to NaOH. Citric acid, being a found for acid-modi®ed shells in the presence of single
weaker acid than phosphoric acid, likely cannot metal ions (Table 1). Phosphoric acid-modi®ed shells
remove lipid on the shell surface. preferentially adsorbed Pb2‡ compared with citric
A comparison between the metal ion uptake ability acid-modi®ed shells. In the case of Cu2‡ adsorption,
of modi®ed shells and commercial cation exchange citric acid-modi®ed shells sequestered signi®cantly
resins showed a number of cases where modi®ed shells more metal ions than phosphoric acid-modi®ed shells.
met or exceeded adsorption by carboxymethylcellu- When comparing modi®ed shells with commercial
lose or Duolite GT-73 (Table 1). This observation was resins, all of the phosphoric acid- and citric acid-
also made by Wafwoyo et al 12 when modi®ed shell modi®ed peanut shells adsorbed signi®cantly more
adsorption was compared with Duolite GT-73 only. Cd2‡ than Duolite GT-73 or Amberlite IRC-718
For Ni2‡, Zn2‡ and Cu2‡ uptake, all unwashed and when cadmium ions were present with other metal
washed, phosphoric acid-treated shells met or ex- ions (Table 2). All of the modi®ed shells were either
ceeded the adsorption of either carboxymethylcellu- similar to or better than carboxymethylcellulose in
lose or Duolite GT-73. Citric acid-modi®ed shells Cd2‡ uptake. For copper ion adsorption, base-
were less consistent in this regard. In all cases except washed, citric acid modi®ed shells were similar to
one, the commercial resins adsorbed more cadmium Duolite GT-73 and carboxymethylcellulose. All modi-
and lead ions than the modi®ed shells. The two ®ed peanut shells adsorbed more copper ions than
Amberlite resins showed signi®cantly higher uptake Amberlite 200, except unwashed, phosphoric acid-
for all ®ve individual metals compared with all of the modi®ed shells, which adsorbed a similar amount.
modi®ed peanut shells. The apparent selectivity of any Reaction with citric acid has been reported to increase
ion exchange resin for a given metal depends upon adsorption of copper ions from solution by the
concentration, the presence of other species and lignocellulosic by-products corn ®ber13 and soybean
pH.14±16 Therefore, comparisons of the effectiveness hulls.15 For Pb2‡, all types of phosphoric acid-modi-
of adsorbents should not be extrapolated beyond the ®ed shells had equivalent or greater adsorption than
systems for which they have been evaluated. Amberlite IRC-718. For Ni2‡ and Zn2‡, none of the
Shells modi®ed with citric or phosphoric acid, modi®ed peanut shells adsorbed as many metal ions as
regardless of wash type, have a preference for copper the commercial resins.
and lead ions.
3.3 Adsorption capacities for modified peanut
3.2 Adsorption of multiple metal ions shells and commercial resins
The presence of multiple metal ions in solution When adsorption capacities for each of the ®ve metals
reduced the adsorption of each metal ion (Table 2) were determined for the modi®ed peanut shells,
compared with only one metal ion in solution (Table signi®cant differences were observed between
1) for all of the modi®ed peanut shell samples and samples that had been water-washed or base-washed,
most of the resins. This result was anticipated because regardless of the type of acid modi®cation (Table 3).
of the competition among the metal ions for limited Apparently, peanut shell adsorption capacities are
binding sites on the shells and resins. In general, base- not dependent upon a particular wash treatment

J Chem Technol Biotechnol 76:593±597 (2001) 595


S Chamarthy, CW Seo, WE Marshall

Metal ion
Adsorbent Cd 2‡ Cu 2‡ Pb 2‡ Ni 2‡ Zn 2‡
Unwashed ± citric acid 0.24bc 0.28c 0.26g 0.13d 0.13e
Unwashed ± phosphoric acid 0.23bcd 0.18de 0.53e 0.14d 0.15de
Water-washed ± citric acid 0.24bc 0.28c 0.29g 0.13d 0.18de
Water-washed ± phosphoric acid 0.27b 0.22d 0.63d 0.16dc 0.20d
Base-washed ± citric acid 0.22cd 0.33b 0.38f 0.19c 0.16de
Base-washed ± phosphoric acid 0.23bcd 0.22d 0.62d 0.16cd 0.17de
Duolite GT-73 0.09e 0.33b 0.97c 0.34b 0.35bc
Amberlite IRC-718 0.05e 2.02a 0.55e 0.41a 0.38b
Amberlite 200 0.36a 0.15fe 1.33b 0.40a 0.47a
Carboxymethylcellulose 0.20cd 0.37b 1.46a 0.33b 0.30c
a
Values (mmoles g 1 dry wt) in the same column with a common subscript are not signi®cantly
Table 2. Adsorption efficienciesa of individual metal different at a = 0.05. Values are means of duplicate determinations where the standard error was
ions by modified peanut shells and commercial <5.0%.
resins in a solution containing all five metal ions Values in boldface represent shell adsorption that meets or exceeds resin adsorption.

before modi®cation. They also do not appear to be ions. In several cases, modi®ed peanut shells had
dependent on a particular acid modi®cation, although better or equal adsorption compared with commercial
base-washed, phosphoric acid-modi®ed shells gener- resins. Phosphoric acid-modi®ed samples generally
ally appear to have greater capacity for select metal had higher adsorption capacities than citric acid-
ions than base-washed, citric acid-modi®ed shells. modi®ed shells. Commercial resins generally had
In almost all cases, the commercial resins had higher adsorption capacities than the experimental
greater adsorption capacities than the acid-modi®ed samples.
peanut shells (Table 3). The notable exception was in This study indicates that inexpensive metal ion
the adsorption capacity for Pb2‡, where citric acid- adsorbents can be developed by acid modi®cation of
modi®ed shells had a greater capacity than Duolite peanut shells, an agricultural waste. These adsorbents
GT-73. show a preference for copper and lead ions and also
show greater adsorption ef®ciency for metal ions than
some commercial resins.
4 CONCLUSIONS
As originally shown by Wafwoyo et al 12 modi®cation
of peanut shells with either phosphoric or citric acid
increased shell adsorption toward metal ions. An ACKNOWLEDGEMENTS
extension of the work by Wafwoyo et al 12 has shown We thank Dr Kanglin Lee (Department of Natural
that phosphoric acid-modi®ed shells possessed gen- Resources and Environmental Design, North Carolina
erally higher metal ion adsorption than citric acid- A&T State University) for his assistance in the
modi®ed shells when the two were compared with a statistical treatment of the data. The research is in
single metal ion at a ®xed concentration of 20 mM. partial ful®lment of a Masters of Science degree for
In the presence of competing metal ions, metal ion one of us (SC) and was supported in part by a research
uptake from solution by the modi®ed peanut shells grant from the USDA-CSREES Capacity Building
depended strongly on the presence of the other metal Program (Grant #95-38814-1729).

Metal ion
2‡ 2‡
Adsorbent Cd Cu Pb 2‡ Ni 2‡ Zn 2‡
Unwashed ± citric acid 0.36d 0.62c 0.84de 0.29d 0.31d
Unwashed ± phosphoric acid 0.37d 0.82c 1.09c 0.30d 0.32d
Water-washed ± citric acid 0.32d 0.69c 0.92cd 0.25d 0.46d
Water-washed ± phosphoric acid 0.50d 0.46d 0.70ef 0.32d 0.43d
Base-washed ± citric acid 0.45d 0.69c 0.47g 0.24d 0.26d
Base-washed ± phosphoric acid 0.48d 0.74c 0.52fg 0.26d 0.53cd
Duolite GT-73 0.94c 0.97bc 0.59fg 0.97c 0.85c
Amberlite IRC-718 2.26a 2.04a 1.45b 2.20a 2.36a
Amberlite 200 1.98b 1.42b 1.65a 1.51b 1.30b
a
Values (mmoles g 1 dry wt) in the same column with a common superscript are not signi®cantly
Table 3. Modified peanut shell and commercial different at a = 0.05. Values for Xm were generated from non-linear least squares analysis of adsorption
resin adsorption capacitiesa (Xm) for individual isotherms developed by means of the Langmuir model.
metal ions Values in boldface represent adsorption maxima that meet or exceed resin adsorption maxima.

596 J Chem Technol Biotechnol 76:593±597 (2001)


Adsorption of toxic metals by modi®ed peanut shells

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