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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


Adsorbent Preparation
from several types of industrial operations is a worldwide
phenomenon [1]. Their removal by various physical, chemi-
Waste tea leaves collected from a cafeteria were washed
cal or biological methods has been repeatedly attempted to
with tap water, dried at 70 C overnight and stored in poly-
overcome the problem. Adsorption by activated carbon re-
thene bags for metal uptake experiments.
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- Metal Uptake in Batch Experiments
ity and high cost effectiveness [5]. By-products of soybean
processing, cottonseed hulls, rice straw, sugarcane bagasse Batch experiments were conducted at 30 C with continu-
[6], bark of Pinus pinaster [7], peanut hulls [8] and paper mill ous shaking at 100 rpm in 500 mL Erlenmeyer flasks, con-
sludge [9] have been tested for their usefulness in the re- taining 200 mL of synthetic solution (pH 5.0), amended
moval of heavy metals from aqueous solutions. Rice straw separately with lead, nickel, iron and zinc at concentrations
and sugarcane bagasse had a Zn adsorption capacity of varying from 5±100 mg/L. Dried waste tea leaves at
0.12 m2/g [6]. Biosorption of heavy metals occurs as a result 0.05±4.00 g/100 mL were used as an adsorbent.
of physicochemical interactions, mainly ion exchange or Samples were drawn at pre-determined time intervals
complex formation between metal ions and the functional from 5±300 min, acidified with conc. HCl and filtered
groups present on the cell surface. Various functional groups through qualitative filter paper (grade 1). Residual metal in
involved are phosphate, carboxyl, amine and amide whose the sorption media was analyzed by an atomic absorption
role in metal binding, however, is still not fully understood spectrophotometer. The metal uptake by the waste tea
[1]. There is a considerable potential for adopting a natural, leaves was calculated as
abundant and economical metal adsorption system, and tea
leaves generated as waste by-product in cafeterias in large Q = (Ci ± Cf) V/1000 M (1)
quantities could be used as an adsorbent for the removal of
heavy metals from aqueous solution. The present paper de- where Q denotes the specific metal uptake [mg/g], V the
scribes the results of using waste tea leaves as an effective volume of the metal solution, Ci and Cf the initial and final
adsorbent for the removal of heavy metals from aqueous so- concentrations of metal in the solution [mg/L], respectively,
lution. 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 100 mg/L of metal containing solution. The biosorption effi-
the column sorption operation, an aqueous solution » 29 mg/ ciency (R) of different metals was different and was higher
L of Pb (pH 5.0) was pumped downward through the column for nickel and zinc at low metal ion concentrations, whereas
at a constant flow rate » 200 mL/h using a peristaltic pump for lead and iron a 96.5 and 79.8 % efficiency, respectively,
(Cole Parmer USA). was obtained. The adsorption of metal by waste tea leaves
The samples, collected from the outlet of the column were was in the order of Pb > Fe > Zn > Ni. It has been shown ear-
analyzed for lead concentration by atomic absorption spec- lier that bark of Pinus pinaster was able to remove 85±90 %
trophotometer. The saturated tea leaves were removed from Pb, 55±85 % Cu and 51±57 % Zn, and waste leaves of differ-
the column, dried and ignited at 600 C to determine lead ent tree species were able to remove 96 % Pb, 61 % Ni and
content in the ash. 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].
Metal (Pb, Fe, Zn and Ni) Analysis

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
Figure 1. Time course of the removal of lead using different concentrations
(g/100 mL) of waste tea leaves.
Infrared spectra of the native as well as metal laden waste Ci: 19 mg/L, pH 5.0; agitation: 100 rpm; temperature: 30 C.
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 Studies concerning the removal of lead, iron and zinc by
samples were encapsulated with potassium bromide to pre- waste tea leaves from a multi-metallic mixture containing
pare translucent sample disks, and the spectra were recorded 30 mg/L of Pb, 21.5 mg/L of Fe and 10 mg/L of Zn revealed
using a Fourier transform infrared spectroscope (BOMEM a 92.5, 84 and 73.2 % removal of Pb, Fe and Zn, respectively,
Hartmann & Braun, Canada). 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
Ash Analysis due to the synergistic effect of Fe and Zn [3, 9], which indi-
cated the interactive regulatory effect of different metallic
Ash analysis was carried out following the procedure men- species in a mixture. Also, a combination of paper mill
tioned in Indian Standard IS 10158 (1982) [10]. 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 Results and Discussion

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
Eng.
Life
Removal of Heavy Metals Sci.

Metal removal by waste tea leaves (see Figs. 1 and 2) is a 3.3 FTIR Spectral Analysis
typical sorption of metals, involving metabolically inert bio-
mass, where metal removal from solution is purely due to Adsorption of heavy metal ions by non-living biomaterials
the chemical and physical sorption, which reaches equilibri- with the involvement of functional groups has been reported
um relatively fast during the initial 0±30 min followed by earlier [22]. Fourier transform infrared spectral analysis (see
diffusion into the sorbent particles which is typically slower Fig. 3) of native biomass of waste tea leaves displayed a
[9, 15±18]. number of absorption peaks corresponding to different func-
tional groups indicating its complex nature with affinity
towards different metallic species [23]. The broad absorption
3.2 Adsorption Isotherms peak at 1651 cm±1 indicated the existence of a carboxyl
(C = O) group and the peak at 2363 cm±1 corresponded to
Langmuir and Freundlich adsorption isotherms [19±20] the amine (NH) group. Also, at 1518 cm±1 a shoulder was
were used to analyze metal sorption from aqueous solution observed which is due to the secondary amide group (see
(see Tab. 1). Langmuir equation valid for monolayer sorp- Fig. 3A). The 1000±1400 cm±1 absorption band corre-
tion onto a surface with a finite number of identical sites is sponded to ±CH3, ±CH2± and C±F groups whereas the
given in Eq. (3): 750±1000 cm±1 band corresponded to S = O, ±C±C± and
C±Cl functional groups.
qeq = Kb Ceq/(1 + b Ceq) (3) On comparing the spectra of lead and iron adsorbed waste
tea-leaves with the native biomass, a broad absorption peak
where K is the maximum amount of the metal ions per unit at 2359±2342 cm±1, corresponding to the amine group, ap-
weight of biomass to form a complete monolayer on the sur- peared and the peak at wave number 1036 cm±1 was reduced
face bound and was determined from the linear plot of and a sharp peak at 760 cm±1 due to the adsorption of iron
Ceq/qeq vs. Ceq. The empirical Freundlich equation based on with the ±C±C± group appeared (see Figs. 3B and E). The
the sorption on a heterogeneous surface is given by Eq. (4): peak(s) [Blockade] observed at wave numbers 765 cm±1,
1740 cm±1 and 2363 cm±1 was reduced as compared to the
qeq = kf Ceq1/n (4) native biomass indicating the involvement of the ±C±C±,
C = O and the amine group in the adsorption of nickel (see
qeq and Ceq have the same meaning as in Langmuir's Fig. 3C). A significantly enlarged peak at 1651 cm±1, corre-
isotherm and kf and n are the Freundlich constants and are sponding to the C = O group, can be seen after the compari-
dependent on environmental factors and are therefore son of the spectra of native and zinc laden biomass (see Fig-
indicators of the adsorption capacity and adsorption s. 3A and D) and demonstrated its possible binding with
intensity, respectively. These constants were determined zinc. Fig. 3F illustrates the spectra of mixed metal (lead, iron
from the linearized Eq. (4) in logarithmic form given as and zinc) laden biomass where the peaks at 2342±2359 cm±1
Eq. (5): and 1651 cm±1 were diminished and the peaks at 767 cm±1
and 823 cm±1 became sharper. The carboxyl groups of the
log (qeq) = (1/n) log Ceq + log kf (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
A good correlation (R2 > 0.9) between the experimental [25] were partially responsible for copper binding. Our stud-
data and Langmuir and Freundlich adsorption models for ies revealed that among different functional groups present
lead, nickel, iron and zinc suggested that the waste tea-leaf on the waste tea leaves, the C = O group played an important
biomass possesses high sorption capacity and high affinity role in the binding of lead and iron, and the amine group in
for metal [21]. the binding of nickel and zinc.

Table 1. Sorption of different metals*.

Equilibrium constants
Metals
Langmuir model Freundlich model
2
K b R kf n R2
[mg/g] [L/mg] [mg/g]

Lead 2.096 0.005 0.975 0.029 1.507 0.958

Iron 79.526 0.001 0.926 0.002 0.765 0.953

Zinc 785.549 0.1316 0.900 0.001 0.699 0.988

Nickel 515.037 0.0817 0.943 0.002 0.632 0.972

* Values of experimental equilibrium constants.

Eng. Life Sci. 2005, 5, No. 1 http://www.els-journal.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 3
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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.

3.4 Lead Sorption in a Downward Continuous Flow Sorption waste tea leaves corresponding to an overall lead sorption
Column efficiency of 73 mg Pb/g dry biosorbent including the only
partially saturated portion from the dynamic sorption zone
In a column packed with 16.3 g of dried biomass of waste still within the column breakthrough (1 mg Pb/L in the out-
tea leaves, 25 L of lead solution containing 29 mg/L of lead let/effluent). Saturated biomass from the column, when
was processed before break through occurred, which was ar- ignited at 600 C for ash analysis, showed an increase in the
bitrarily established at 1.0 mg/L of lead in the column outlet inorganic content from 4.0±6.2 % due to lead adsorption and
(see Fig. 4). contained 0.046 mg of lead/g of ash. Therefore, metal laden
During the column residence time of 15 min, an amount biomass can be disposed off by incineration and the ash can
of 1192 mg of lead was adsorbed by 16.3 g of dry biomass of be directed to restricted area land-fills.

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Eng.
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Removal of Heavy Metals Sci.

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