Eng.

Life
Removal of Heavy Metals Sci.

Removal of Heavy Metals by Waste Tea Leaves from Aqueous

Solution
By S. S. Ahluwalia and D. Goya*

In this paper, tea leaves were shown to be an effective, low-cost biosorbent. Removal of lead, iron, zinc and nickel from
20 mg/L metal solution by dried biomass of waste tea leaves amounted to 96, 91, 72 and 58 %, respectively, at equilibrium,
which followed Langmuir and Freundlich adsorption isotherms. Adsorption of metal was in the order of Pb > Fe > Zn > Ni
from 5±100 mg/L of metal solution. From a multi-metallic mixture, 92.5, 84 and 73.2 % of lead, iron and zinc, respectively,
were removed. Fourier transform infrared (FTIR) studies indicated that the carboxyl group was involved in the binding of
lead and iron, whereas the amine group was involved in the binding of nickel and zinc. A flow through sorption column
packed with dried biomass demonstrated a sorption capacity of 73 mg Pb/g of biomass, indicating its potential in cleaning me-
tal containing wastewater. The metal laden biomass obtained could be disposed off by incineration.

1 Introduction 2 Materials and Methods

Contamination of the environment by toxic heavy metals

from several types of industrial operations is a worldwide
phenomenon [1]. Their removal by various physical, chemi-
cal or biological methods has been repeatedly attempted to
overcome the problem. Adsorption by activated carbon re-
moves traces of heavy metals, but is highly cost intensive
[2, 3]. Bio-wastes as sorbents [4] have recently gained impor-
tance because of their comparable efficiency, easy availabil-
ity and high cost effectiveness [5]. By-products of soybean
processing, cottonseed hulls, rice straw, sugarcane bagasse
[6], bark of Pinus pinaster [7], peanut hulls [8] and paper mill
sludge [9] have been tested for their usefulness in the re-
moval of heavy metals from aqueous solutions. Rice straw
and sugarcane bagasse had a Zn adsorption capacity of
0.12 m2/g [6]. Biosorption of heavy metals occurs as a result
of physicochemical interactions, mainly ion exchange or
complex formation between metal ions and the functional
groups present on the cell surface. Various functional groups
involved are phosphate, carboxyl, amine and amide whose
role in metal binding, however, is still not fully understood
[1]. There is a considerable potential for adopting a natural,
abundant and economical metal adsorption system, and tea
leaves generated as waste by-product in cafeterias in large
quantities could be used as an adsorbent for the removal of
heavy metals from aqueous solution. The present paper de-
scribes the results of using waste tea leaves as an effective
adsorbent for the removal of heavy metals from aqueous so-
lution.
Adsorbent Preparation
Waste tea leaves collected from a cafeteria were washed
with tap water, dried at 70 C overnight and stored in poly-
thene bags for metal uptake experiments.
Metal Uptake in Batch Experiments
Batch experiments were conducted at 30 C with continu-
ous shaking at 100 rpm in 500 mL Erlenmeyer flasks, con-
taining 200 mL of synthetic solution (pH 5.0), amended
separately with lead, nickel, iron and zinc at concentrations
varying from 5±100 mg/L. Dried waste tea leaves at
0.05±4.00 g/100 mL were used as an adsorbent.
Samples were drawn at pre-determined time intervals
from 5±300 min, acidified with conc. HCl and filtered
through qualitative filter paper (grade 1). Residual metal in
the sorption media was analyzed by an atomic absorption
spectrophotometer. The metal uptake by the waste tea
leaves was calculated as
Q = (Ci ± Cf) V/1000 M (1)
where Q denotes the specific metal uptake [mg/g], V the
volume of the metal solution, Ci and Cf the initial and final
concentrations of metal in the solution [mg/L], respectively,
and M the dry weight of the waste tea leaves taken for ad-
sorption [g] [2, 3].
Similarly, biosorption efficiency R [%] was calculated as

R = 100 ” (Ci ± Cf)/Ci (2)

± Lead Uptake in a Continuous Flow Sorption Column

[*] S. S. Ahluwalia, D. Goyal (author to whom correspondence should be
addressed, e-mail: d_goyal_2000@yahoo.com), Thapar Institute of En- For continuous flow lead adsorption studies, a laboratory
gineering & Technology, Department of Biotechnology & Environmental
Sciences, Patiala 147 004, Punjab, India. scale acrylic column of 2 cm diameter and 10 cm length was

Eng. Life Sci. 2005, 5, No. 2 DOI: 10.1002/elsc.200420066  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1
Eng.
Life
Sci. Full Paper

packed with 16.3 g of dried waste tea-leaf biomass. During
the column sorption operation, an aqueous solution » 29 mg/
L of Pb (pH 5.0) was pumped downward through the column
at a constant flow rate » 200 mL/h using a peristaltic pump
(Cole Parmer USA).
The samples, collected from the outlet of the column were
analyzed for lead concentration by atomic absorption spec-
trophotometer. The saturated tea leaves were removed from
the column, dried and ignited at 600 C to determine lead
content in the ash.
Metal (Pb, Fe, Zn and Ni) Analysis
100 mg/L of metal containing solution. The biosorption effi-
ciency (R) of different metals was different and was higher
for nickel and zinc at low metal ion concentrations, whereas
for lead and iron a 96.5 and 79.8 % efficiency, respectively,
was obtained. The adsorption of metal by waste tea leaves
was in the order of Pb > Fe > Zn > Ni. It has been shown ear-
lier that bark of Pinus pinaster was able to remove 85±90 %
Pb, 55±85 % Cu and 51±57 % Zn, and waste leaves of differ-
ent tree species were able to remove 96 % Pb, 61 % Ni and
71.3 % Zn from 50 mg/L of metal solutions [7]. The pH in
the range of 4±5 supported the maximum metal biosorption
[3, 11], whereas the temperature had no influence [12, 13].

The samples were acidified with 2±3 drops of concen-

trated HCl, filtered and centrifuged, when necessary. There-
after, the residual metal content in the sorption medium was
analyzed by means of an atomic absorption spectrophotome-
ter (GBC 932AA, Australia) using an air-acetylene flame.
The stock solution of 1000 mg/L of each metal was procured
from Acros organics, New Jersey, USA, and the appropriate
dilutions were made by milli Q water as per the GBC cata-
logue.

FTIR Analysis
Infrared spectra of the native as well as metal laden waste
tea leaves were obtained after drying the biomass at 70 C.
Fourier transform infrared studies of mixed metal laden
waste tea leaves were also carried out. The finely powdered
samples were encapsulated with potassium bromide to pre-
pare translucent sample disks, and the spectra were recorded
using a Fourier transform infrared spectroscope (BOMEM
Hartmann & Braun, Canada).
Ash Analysis
Ash analysis was carried out following the procedure men-
tioned in Indian Standard IS 10158 (1982) [10].
3 Results and Discussion
Figure 1. Time course of the removal of lead using different concentrations
(g/100 mL) of waste tea leaves.
Ci: 19 mg/L, pH 5.0; agitation: 100 rpm; temperature: 30 C.
Studies concerning the removal of lead, iron and zinc by
waste tea leaves from a multi-metallic mixture containing
30 mg/L of Pb, 21.5 mg/L of Fe and 10 mg/L of Zn revealed
a 92.5, 84 and 73.2 % removal of Pb, Fe and Zn, respectively,
within 15 min and reached equilibrium in 60 min of contact
with the adsorbent (see Fig. 2). From the multi-metallic mix-
ture lead dominated competitive binding, which might be
due to the synergistic effect of Fe and Zn [3, 9], which indi-
cated the interactive regulatory effect of different metallic
species in a mixture. Also, a combination of paper mill
sludge and microbial bio-waste has been shown to be effec-
tive in the simultaneous removal of 93 % Pb, 87 % Zn and
76 % Ni from a multi-metallic solution [14].

3.1 Adsorption of Lead, Iron, Nickel and Zinc from Single and
Multi-Metal Synthetic Mixture

Adsorption of lead was a function of the biomass concen-

tration, and 50 % of the equilibrium uptake occurred in the
first 30 min of contact with the adsorbent (see Fig. 1). At
equilibrium, 96, 91, 72 and 58 % of lead, zinc, iron and
nickel, respectively, were removed from 20 mg/L of each
metal containing solution (pH 5.0) separately at ambient
temperature by 0.5 g of dried waste tea leaves per 100 mL.
The specific metal uptake by the biomass increased with an
Figure 2. Time course of the adsorption of Pb, Fe and Zn from a mixed metal
increase in metal concentration and it amounted to 8.6, 4.9, solution using 0.5 g waste tea leaves.
11.4 and 23.2 mg/g for Pb, Ni, Zn and Fe, respectively, from Ci: Pb: 30 mg/L; Fe: 21.5 mg/L; Zn: 9 mg/L.

2  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.els-journal.de Eng. Life Sci. 2005, 5, No. 2

Metal removal by waste tea leaves (see Figs. 1 and 2) is a
typical sorption of metals, involving metabolically inert bio-
mass, where metal removal from solution is purely due to
the chemical and physical sorption, which reaches equilibri-
um relatively fast during the initial 0±30 min followed by
diffusion into the sorbent particles which is typically slower
[9, 15±18].
3.2 Adsorption Isotherms
Langmuir and Freundlich adsorption isotherms [19±20]
were used to analyze metal sorption from aqueous solution
(see Tab. 1). Langmuir equation valid for monolayer sorp-
tion onto a surface with a finite number of identical sites is
given in Eq. (3):
qeq = Kb Ceq/(1 + b Ceq)
where K is the maximum amount of the metal ions per unit
weight of biomass to form a complete monolayer on the sur-
face bound and was determined from the linear plot of
Ceq/qeq vs. Ceq. The empirical Freundlich equation based on
the sorption on a heterogeneous surface is given by Eq. (4):
qeq = kf Ceq1/n
qeq and Ceq have the same meaning as in Langmuir's
isotherm and kf and n are the Freundlich constants and are
dependent on environmental factors and are therefore
indicators of the adsorption capacity and adsorption
intensity, respectively. These constants were determined
from the linearized Eq. (4) in logarithmic form given as
Eq. (5):
log (qeq) = (1/n) log Ceq + log kf
A good correlation (R2 > 0.9) between the experimental
data and Langmuir and Freundlich adsorption models for
lead, nickel, iron and zinc suggested that the waste tea-leaf
biomass possesses high sorption capacity and high affinity
for metal [21].
Table 1. Sorption of different metals*.
Metals
Langmuir model
K b
[mg/g] [L/mg]
Lead 2.096 0.005
Iron 79.526 0.001
Zinc 785.549 0.1316
Nickel 515.037 0.0817
* Values of experimental equilibrium constants.
Eng. Life Sci. 2005, 5, No. 1 http://www.els-journal.de
Eng.
Life
Removal of Heavy Metals Sci.
3.3 FTIR Spectral Analysis
Adsorption of heavy metal ions by non-living biomaterials
with the involvement of functional groups has been reported
earlier [22]. Fourier transform infrared spectral analysis (see
Fig. 3) of native biomass of waste tea leaves displayed a
number of absorption peaks corresponding to different func-
tional groups indicating its complex nature with affinity
towards different metallic species [23]. The broad absorption
peak at 1651 cm±1 indicated the existence of a carboxyl
(C = O) group and the peak at 2363 cm±1 corresponded to
the amine (NH) group. Also, at 1518 cm±1 a shoulder was
observed which is due to the secondary amide group (see
Fig. 3A). The 1000±1400 cm±1 absorption band corre-
sponded to ±CH3, ±CH2± and C±F groups whereas the
750±1000 cm±1 band corresponded to S = O, ±C±C± and
C±Cl functional groups.
(3) On comparing the spectra of lead and iron adsorbed waste
tea-leaves with the native biomass, a broad absorption peak
at 2359±2342 cm±1, corresponding to the amine group, ap-
peared and the peak at wave number 1036 cm±1 was reduced
and a sharp peak at 760 cm±1 due to the adsorption of iron
with the ±C±C± group appeared (see Figs. 3B and E). The
peak(s) [Blockade] observed at wave numbers 765 cm±1,
1740 cm±1 and 2363 cm±1 was reduced as compared to the
(4) native biomass indicating the involvement of the ±C±C±,
C = O and the amine group in the adsorption of nickel (see
Fig. 3C). A significantly enlarged peak at 1651 cm±1, corre-
sponding to the C = O group, can be seen after the compari-
son of the spectra of native and zinc laden biomass (see Fig-
s. 3A and D) and demonstrated its possible binding with
zinc. Fig. 3F illustrates the spectra of mixed metal (lead, iron
and zinc) laden biomass where the peaks at 2342±2359 cm±1
and 1651 cm±1 were diminished and the peaks at 767 cm±1
and 823 cm±1 became sharper. The carboxyl groups of the
(5) alfalfa biomass [24] were involved in the binding of Cd(II),
Cr(III), Pb(II) and Zn(II) and those of dead algal biomass
[25] were partially responsible for copper binding. Our stud-
ies revealed that among different functional groups present
on the waste tea leaves, the C = O group played an important
role in the binding of lead and iron, and the amine group in
the binding of nickel and zinc.
Equilibrium constants
Freundlich model
2
R kf n R2
[mg/g]
0.975 0.029 1.507 0.958
0.926 0.002 0.765 0.953
0.900 0.001 0.699 0.988
0.943 0.002 0.632 0.972
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 3
Eng.
Life
Sci. Full Paper
3.4 Lead Sorption in a Downward Continuous Flow Sorption
Column
In a column packed with 16.3 g of dried biomass of waste
tea leaves, 25 L of lead solution containing 29 mg/L of lead
was processed before break through occurred, which was ar-
bitrarily established at 1.0 mg/L of lead in the column outlet
(see Fig. 4).
During the column residence time of 15 min, an amount
of 1192 mg of lead was adsorbed by 16.3 g of dry biomass of
4  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 3. FTIR spectra of waste tea leaves.
A: native; B: Pb laden; C: Ni laden; D: Zn
laden; E: Fe laden; F: mixture of Pb, Fe
and Zn laden.
waste tea leaves corresponding to an overall lead sorption
efficiency of 73 mg Pb/g dry biosorbent including the only
partially saturated portion from the dynamic sorption zone
still within the column breakthrough (1 mg Pb/L in the out-
let/effluent). Saturated biomass from the column, when
ignited at 600 C for ash analysis, showed an increase in the
inorganic content from 4.0±6.2 % due to lead adsorption and
contained 0.046 mg of lead/g of ash. Therefore, metal laden
biomass can be disposed off by incineration and the ash can
be directed to restricted area land-fills.
http://www.els-journal.de Eng. Life Sci. 2005, 5, No. 2

Figure 4. Sorption column break-through curve.
Inlet concentration of Pb: 29 mg/L, pH 5.0; Flow rate: 200 mL/h; Dry biomass:
16.3 g.
Acknowledgements
The authors would like to thank the Director of the Tha-
par Institute of Engineering & Technology, Patiala (Punjab),
for providing the facilities and necessary support. They are
also thankful to the Council of Scientific & Industrial Re-
search (CSIR), New Delhi, for funding the project.
Received: August 9, 2004 [ELS 66]
Received in revised form: February 7, 2005
Accepted: February 23, 2005
References
[1] A. Kapoor, T. Viraraghavan, Heavy metal biosorption sites in
Aspergillus niger, Biores. Technol. 1997, 61, 221±227.
[2] H. Niu, X. S. Xu, J. H. Wang, Removal of lead from aqueous solutions by
Penicillium biomass, Biotechnol. Bioeng. 1993, 42, 785±787.
[3] Y. Sag, T. Kutsal, The simultaneous biosorption process of lead (II) and
nickel (II) on Rhizopus arrhizus, Process Biochem. 1997, 32, 591±597.
[4] L. Rome, G. M. Gadd, Use of pelleted and immobilized yeast and fungal
biomass for heavy metal and radionuclides, J. Ind. Microbiol. 1991, 7,
97±99.
[5] S. Schiewer, B. Volesky, Modeling multi-metal ion exchange in
biosorption, Environ. Sci. Technol. 1996, 30, 2921±2927.
[6] W. E. Marshall, E. T. Champagne, Agricultural by-products as adsor-
bents for metal ions in laboratory prepared solutions and in manufactur-
ing wastewater, J. Environ. Sci. Health, Part A: Sci. & Eng. 1995, 30 (2),
241±246.
______________________
Eng. Life Sci. 2005, 5, No. 1 http://www.els-journal.de
Eng.
Life
Removal of Heavy Metals Sci.
[7] G. Vazquez, G. Antorrena, J. Gonzalez, M. D. Doval, Adsorption of
heavy metal ions by chemically modified Pinus pinaster bark, Biores.
Technol. 1994, 48 (3), 251±255.
[8] K. Periasamy, C. Namasivayam, Process development for removal and
recovery of cadmium from wastewater by a low cost adsorbent:
Adsorption rates and equilibrium studies, Ind. Eng. Chem. Res. 1994,
33 (2), 317±320.
[9] S. S. Ahluwalia, D. Goyal, Utilization of paper mill sludge for removal of
heavy metals from aqueous solution, Res. J. Chem. Environ. 2004, 8 (2),
34±37.
[10] IS 10158, Methods of Analysis of Solid Waste (Excluding industrial solid
waste), 1982.
[11] S. Y. Quek, D. A. J. Wase, C. F. Forster, The use of sago waste for the
sorption of lead and copper, Water SA. 1998, 24 (3), 251±256.
[12] D. Sanyahumbi, J. R. Duncan, M. Zhao, R. van Hile, Removal of lead
from solution by the non-viable biomass of the water fern Azolla
filiculoides, Biotechnol. Lett. 1998, 20, 745±747.
[13] K. S. Low, C. K. Lee, A. C. Leo, Removal of metals from electroplating
waste using banana pith, Bioresource Technol. 1995, 44, 109±112.
[14] N. Joshi, S. S. Ahluwalia, D. Goyal, Removal of heavy metals from
aqueous solution by different bio-wastes materials, Res. J. Chem.
Environ. 2003, 7 (4), 26±30.
[15] S. E. Schumate, G. W. Strandberg, I. Parrot, Biological removal of metal
ions from aqueous process streams, Appl. Microbiol. Biotechnol. 1995,
42, 807±811.
[16] Z. Aksu, T. Kutsal, A comparative study for biosorption characteristic
of heavy metals ions with C. vulgaris, Environ. Technol. 1990, 11,
979±987.
[17] M. J. Brown, Metal recovery and processing, In Biotechnology, The
Science and the Business (Eds V. Moses, R. E. Cape), Harvard Academic
Publishers, New York 1991, 1±4.
[18] D. Brady, A. D. Stoll, L. Starke, J. R. Duncan, Chemical and enzymatic
extraction of heavy metal binding polymers from isolated cell walls of
Saccharomyces cerevisiae, Biotechnol. Bioeng. 1994, 44, 297±302.
[19] Z. Aksu, Biosorption of heavy metals by microalgae in batch
and continuous system, In Algae for Wastewater Treatment (Eds Y. S.
Wong, N. F. Y. Tam), Springer Verlag and Landes Biosciences, Berlin
1998.
[20] G. C. Donmez, Z. Aksu, A. Ozturk, T. Kutsal, A comparative study on
heavy metal biosorption characteristics of some algae, Process Biochem.
1994, 34, 885±892.
[21] B. Volesky, S. Schiewer, Biosorption, Metals in Encyclopedia of
Bioprocess Technology (Fermentation, Biocatalysis and Bioseparation),
Vol. 1, John Wiley, New York 1999, 433±453.
[22] C. R. R. Nagendra, L. Lyengar, C. Venkobachar, Sorption of copper (II)
from aqueous phase by waste biomass, J. Environ. Eng. 1993, 119,
260±265.
[23] T. Viraraghavan, R. Saskatchewan, M. M. Dronamraju, Removal of
copper, nickel and zinc from wastewater by adsorption using peat,
J. Environ. Sci. Health 1993, A28, 1261±1265.
[24] J. L. Gardea-Torresdey, K. J. Tiemann, J. H. Gonzalez, O. Rodriguez,
G. Gamez, Phytofiltration of hazardous cadmium, chromium, lead and
zinc ions by biomass of Medicago sativa (Alfalfa), J. Haz. Mat. 1998, 57,
29±39.
[25] J. L. Gardea-Torresdey, M. K. Becker-Hapak, J. M.Hosea, D. W. Darnall,
Effect of chemical modification of algal carboxyl groups on metal ion
binding, Environ. Sci. Technol. 1990, 24, 1372±1378.
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 5