� Proceedings of the . """"""o....., organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th _26th, July, 2013. IL.�
"International Conference on AdvancedNanomaterials & Emerging Engineering Technologies" (ICANMEET-20/3)
•
Adsorption of Copper (Ii) and Nickel (Ii) Ions from Metal Solution using Graft Copolymer of Cellulose Extracted from The Sisal Fiber with Acrylonitrile Monomer #i $2 $3 Hajeeth, T. ,Gomathi, T. , Sudha, p.N. #
Department of chemistry, Sathyabama University, Chennai, Tamilnadu, india
PO & Research department of chemisliY, DKM College for women, Vellore, Tamilnadu, india '
[email protected] [email protected] [email protected]
$
Abstract - This study mainly concerns with the removal of heavy metal ions such as copper and nickel from aqueous solution with the prepared cellulose graft acrylonitrile as an adsorbent using adsorption process .The effect of pH, contact time, and initial adsorbent dosage on the metal ion adsorption capacity was investigated. The obtained results indicate that the adsorption amount of heavy metal ions increased with the increase of shaking time, adsorbent dose and pH of the media which revealed that the optimum pH and adsorbent dosage for both Cu(II) and Ni(II) was found to be pH 5 and 4 gm. The optimum contact time for copper and nickel metal ion was observed to be around 200 minutes and 240 minutes. The experimental results were examined using the Langmuir and Freundlich isotherms to obtain the appropriate model. The observed results indicate that the Freundlich equation was the best model for both Cu(II) ion and Ni(II). From the above results it was concluded that the cellulose graft acrylonitrile copolymer was
found
to
be
the
efficient
adsorbent
for
copper(II) and nickel (II) under optimum conditions.
I. INTRODUCTION One of the essential materials which were present in numerous areas of application such as machine industry, chemical industry, and plating industry was the metal ions (Warshawsky et aI., 1988).Through the fossil fuel combustion, smelting and the mining process the heavy metal ions can enter into the environment (Carson et aI., 1986; Bewley, 1980; Micera and Dessi, 1988). But because of the toxic nature and other adverse effects on many life forms there have been of great concern for the heavy metal ions in the environment. Nowadays the heavy metal contamination of the environment has become a serious problem which was due to the greater amount of industrial activities. The contamination caused by the heavy metal has become a main critical problem recently because the metals gets persisted and accumulated in the environment which may cause many health problems including dehydration, lung and eye irritation , nausea, stomach ache, dizziness and damage to the nervous system (Weng et aI., 1994).
978-1-4799-1379-4/13/$31.00©2013 IEEE
Removal of heavy metal pollutants from the contaminated water was done using various treatment techniques such as ion-exchange, reverse osmosis, adsorption, complexation, and precipitation (Volesky et aI., 1995;Crist et aI., 1996).Among the various treatments proposed currently, the adsorption is one of the most popular methods which was considered as an effective, efficient and economic method for wastewater purification (Ghuxia Zhaio et aI., 2011).In the recent years, there is an increasing interest in the application of biological materials in the removal of heavy metal ions from aqueous solutions. Since the cost of the materials which is having biological origin is much lower than the cost of commercial adsorbents, such as activated carbon or ion-exchange resins, the prepared biological materials might gain a special attention(AI-Omair et al.,2007).The application of low-cost sorbents has been widely studied for metal removal from water (Abdel ghani et aI., 2004).Most of the adsorbents were developed based on their interactions with the functional groups on the surfaces of the adsorbents. The functional groups present in the adsorbents have important effects on the reusability and capacity for the metal ion removal and as well as the effectiveness (Rivas et al.,2002 ).The polymeric adsorbents having insoluble nature with different functional groups complexes with metal ions which have become well-known for the removal of metal cations from aqueous solutions (Wan Ngah et al.,2002;George et aI., 1999). Several adsorbents such as sawdust, silica, iron oxide, wheat shell, bagasse, fly ash, spent activated clay, natural kaolonite clay, modified goethite and natural fibers were used(Ajmal et al.,1998; Gupta et al.,2000; Weng et al 2008; Bascil et al.,2004; Chojnaka et al.,2005). Sisal fiber is one of the natural fiber often used as adsorbent in waste water treatment. The main constituent present in all the plants was the cellulose. So many processes were used to extract high-purified microfibrils from the cell wall. They are generally based on successive chemical and mechanical treatments.
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1a; ;uJ Proceedings of the : � �1l\iI 20J3) organized by Sathyabama Umverslty, Chennal, IndIa In assocIatIOn wIth DRDO, New Deihl, indIa, 24 -26, July, 2013.
"International Conference on AdvancedNanomaterials & Emerging Engineering Techn� ogi {," (ICANMEET
Laol!llllll.!l lMJ lll
A plenty of research work was carried out to study the kinetics, mechanism and thermodynamics of sorption. In the present work, the cellulose was first extracted from the sisal fiber and then to that extracted cellulose the grafting was done with the acrylonitrile monomer using the redox initiator ceric ammonium nitrate. The batch adsorption studies was carried out with the prepared cellulose-g acrylonitrile copolymer to study the removal of Cu2+ and Ni2+from aqueous solution. In addition to this, the optimum parameters affecting the metal ions uptake e.g. Temperature, pH of the solution, different concentrations of metal ion was also manifested.
from acid (Juan Morain et a!., 2008; Susheel Kaila et al.,2011) E.
Mechanical Treatment of the Processed Fibers
The acidically treated fibers was suspended in water and then stirred well using a mechanical stirrer of type RQ 1.27 A at a speed of 8000 R.P.M. for 4 h. The suspension was then finally kept in an oven at 90°C till it was dry. F.
Preparation ofgrafted co-polymer
The sisal fiber was purchased from the local farms. The analytical grade reagents such as NaOH, acetic acid, sodium hypochlorite, oxalic acid, ceric ammonium nitrate, acrylonitrile and nitric acid were obtained from Central Drug House Pvt Ltd. For the metal ion removal studies, the stock solutions of copper (II) and nickel (II) (200 mg/L) were prepared by dissolving NiCh and CuS04.5H20 (procured from Merck, India) in double distilled water. All the chemicals used were of analytical reagent grade.
The cellulose extracted from the sisal fiber (lg) was added to 100ml of water and stirred well to form a homogeneous suspension. Iml of acrylonitrile monomer dissolved in 20 ml of water was then added to that homogenous solution. To initiate the polymerization process in the above mixture the redox initiator ceric ammonium nitrate (0.5 g of CAN in lOml of IN HN03) was added. After all the addition was over, the above mixture was heated to 70°C. Simultaneously this hot solution was stirred using a magnetic stirrer for approximately 30 minutes.After a certain period of time the above solution was poured into excess sodium hydroxide (2N) solution to precipitate the graft copolymer. Finally, the obtained graft copolymer precipitate was then filtered, dried and weighed.
B. Preparation of Steam Exploded Fibers.
G.
The sisal fibers (30 g) were chopped into uniform sizes (lOcm). Then to the chopped fibers taken in a beaker, 2% NaOH (fiber to liquor ratio 1:10) solution was added. This mixture was then placed in an autoclave for a period of 1 hr which was maintained at a pressure of 20 lb. After a certain period of time, the pressure was released immediately. Then fibers were removed from the autoclave which was then washed with water till they were rid of alkali. The washed fibers were allowed to drain off free from water.
Investigation was done to study the extent of adsorption with different concentrations of copper sulphate and nickel chloride using batch adsorption technique. The extent of removal of the metals was examined separately by changing the pH of solution, adsorbent dosage, and time of shaking of the adsorbent metal solution mixture. About 1 g of cellulose-g-acrylonitrile copolymer was treated with 100 ml of the prepared copper sulphate and nickel chloride solutions separately. These solutions were taken in stoppered bottles and it was then agitated at 30°C using orbital shaker at fixed rate of 160 rpm.The adsorbent was separated by filtration using whattman filter paper and the aqueous phase concentration of metal was determined with atomic adsorption technique .A similar procedure was carried out at various time intervals, adsorbent doses and pH. Using either the sodium hydroxide or the hydrochloric acid the pH of each solution was adjusted to different values.
II. MATERIALS AND METHODS
A. Materials
C.
Preparation of Steam Exploded Bleached Fibers.
The bleaching process of the steam exploded fibers was carried out using a mixture of NaOH and acetic acid (27 and 78.8 g, respectively) and a mixture of 1:3 sodium hypochlorite solution. This treatment was then repeated for approximately six times. After this process is over, the fibers were thoroughly washed in distilled water and dried.
D. Preparation of Steam Exploded Fibers in Acidic Medium.
Experimental process of removal of copper and nickel
III. RESULTS AND DISCUSSION
The steam exploded bleached fibers taken in an autoclave was treated with different concentrations of oxalic acid such as 5%, 7%, 9%, and 11% until it attained a pressure of 20 lb. After it attains that particular pressure the pressure was released immediately.The autoclave was again set to reach a pressure of 20 lb, and the fibers were kept under that pressure for 15 min. The pressure was released and the process repeated 8 times. The fibers were taken out, washed till the washings no longer decolorized KMn04 solution to make sure that the washings were free
A. Effect of adsorbent dose The effect of the adsorbent dose was studied at room temperature by varying the sorbent amounts from 1 to 5 g. For all these runs, initial concentration of copper and nickel was fixed as 200 mg/L. Figure (1) represents the effect of adsorbent dose on the adsorption of Cu2+ and Ni2+ ions by keeping the other parameters such as contact time and pH of solution as constant. From the above figures it was observed that the adsorption of copper and nickel increases rapidly with increase in the amount of cellulose
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� Proceedings of the
"International Conference on AdvancedNanomalerials & Emerging Engineering Technologies" (ICANMEET
.� ,--,...._t.:J _ . 20J3) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, lndia, 24ht .
_26th, July, 2013.
+
graft acrylonitrile (adsorbent) which was due to the greater availability of the surface area at higher concentration of the adsorbent. But after a certain amount of adsorbent was added (4g-6g) it showed no further increase in adsorption. Further addition of the adsorbent beyond this (4g) did not cause any significant change in the adsorption. This may be due to overlapping of adsorption sites as a result of overcrowding of adsorbent particles (Namasivaayam et aI., 1998).From the results, it is revealed that the maximum removal of copper and nickel was obtained in the adsorbent dose of 4g.
� 100
- Copper ... Nickel
z "C I: '" + N :::I U 0
Cij
> 0
E
80 60 40 20
G> 0::
0
*
0
100
200 300 Time in minutes
400
+
� 100 "0 I: '" + N :::I U
Figure (2)-Effeet ofeontaet time on the removal of en 2+ and Ni 2+
- Copper ... Nickel
z
80
C.
60
'0 40 Cij > 0
E
G> 0:: :Je. 0
20 0
0
2 4 6 Adsorbent dose (9)
8
Figure (I )-Effect of adsorbent dose on the removal of Cu 2+ and Ni 2
B. Effect of contact time Equilibrium time is one of the important parameters for an economical wastewater treatment system. After optimization of the bioadsorbent dose of Ig per 200 ml test solution for both copper and nickel ion solution the effect of contact time for the efficient removal of metal ions was studied. Figure (2) clarifies the effect of contact time on the adsorption of Cu2+ and Ni2+ ions onto the cellulose graft acrylonitrile .The adsorption of copper and nickel was measured at five different contact time from 60minutes to 360 minutes. From the results of figure-(2) it was evident that the removal of Cu (II) and Ni (II) increased with increase in the contact time and reached a maximum at 200min in case of copper(lI) and 240 minutes in case of nickel(II).After a certain time of contact further increase in contact time did not bring about any improvement (Oyedeji et al.,201O). At the equilibrium time the metal ion uptake of 55.6% for Ni(lI) and 74.1% for Cu(lI) were achieved. The initially increased uptake of both metal ions with increase in contact time can be due to the decreased mass transfer coefficient of the diffusion controlled reaction between the adsorbent and the metal ion (El sayed et al.,2010).After some extent further increase in contact time shows a insignificant decrease in the uptake which may be due to a quick exhaustion of the adsorption sites(Singanan et aI., 2011).
Effect of pH
The removing ability of copper and nickel ions by the adsorbent mainly depends on the pH of the solution and this depends on the ion state and nature of the material. The effect of pH on the adsorption of Cu(lI) and Ni(lI) onto the cellulose graft acrylonitrile copolymer was shown in figure-(3).The results presented in the figure-(3) indicate that the adsorption increases initially with an increase in pH of the metal ion solution but thereafter it shows a decrease. In both Cu (II) ions and Ni (II) ions the optimum pH was observed to be 5. The initial increase in the metal ion removal with increasing pH was due to the fact that at lower pH values the metal ions are more and this will enhances their adsorption as observed by Olayinka et al. (2009). At a higher pH value, binding sites start deprotonating and makes different function groups available for metal binding. Decrease in adsorption at higher pH was due to formation of soluble hydroxide which results in the formation of precipitates. This is consistent with the observation of Lisa et aI., 2004 and Xiao and Ju-Chang, 2009. +
� 100 z "C I: '" + N :::I U
- Copper ... Nickel
80 60
'0 40 Cij > 0
E 20
G> 0::
*
0
0
2
4
6
8
10
pH
Figure (3) -Effect of pH on the removal of Cu 2+ and Ni 2+
D. Biosorption isotherms The adsorption behavior of solutes on adsorbents was very well described in terms of the adsorption isotherms.In the present project work, the Langmuir and the freundlich isotherm models were selected and studied. One of the important assumption of Langmuir adsorption isotherm was that the adsorption occurs at specific homogeneous sites within the biosorbent. This model assumes the
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� Proceedings of the : ._1!J 3I!I!_ . 20J3) organized by Sathyabama Umverslty, Chennal, IndIa In assocIatIOn wIth DRDO, New Deihl, lndIa, 24 -26, July, 2013. IL:�
"International Conference on AdvancedNanomaterials & Emerging Engineering Techn� ogi�{," (ICANMEET Metalions
monolayer adsorption without any interaction between adsorbed ions.The most general form of the Langmuir equation was given as follows Cads
=
(KLCeq)/(1 + bCeq
(1)
The linear form of the Langmuir equation can be written as given below Ceq/Cads
=
bCeq/KL + lIKL
Cmax
=
(2)
(3)
K db
where Cads = amount of metal ion adsorbed (mg·g- I), Ceq = equilibrium concentration of metal ion in solution (mg'dm-3), KL = Langmuir constant (dm3·g-1 ), b = Langmuir constant (dm3·mg-l), Cmax = maximum metal ion adsorbed corresponding to the saturation capacity of the biosorbent, The constant b present in the above equation describes the energy or the net enthalpy of the adsorption process.The constants KL and b are the characteristics of the Langmuir isotherm and it can be determined from the linear form of Langmuir equation (2). Using the constant KL the enthalpy of adsorption can be determined (Schmuchl et aI., 2001). A plot of Ceq versus Ceq/Cads gives a straight line of slope (b/Kdand intercept (lIKL )' The langmuir adsorption isotherm of the sorption of copper and nickel ions by cellulose graft acrylonitrile copolymer was represented in the figure-4 and figure5.The data fit the Langmuir isotherms model well for Cu(lI) and Ni (II) ions (Figure-4 and 5).The values of Langmuir parameters for the removal of both Cu(lI) and Ni (II) metals ions are presented in Table l. Copper(lI)
4
o,+-------�--�--� o
100
200
Figure (4)-Langmuir isotherm for CU(Il) ion removal on Cellulose-g Acrylonitrile copolymer 6.0
Nickei(li)
W 5.5 � � 5.0
C,nux(mglg)
Cu(II)
2.428
0.004873
498.26
Ni(II)
4. 386
0. 002478
1769. 98
The correlation coefficient (R2) for the biosorption of Cu (II) and Ni (II) are 0.642 and 0.608, respectively. The linearity of the above plots indicates application of the Langmuir equation, supporting monolayer formation on the surface of the biosorption. The biosorption of the metal ions depends on the concentration and pH which was identified from the b and KL values. The isotherm is beginning to reach a plateau, which can typically be described by the Langmuir isotherm (Parfitt and Rochester, 1983) The separation constant or equilibrium constant (Dimensionless form)(RL) can be used to express the essential feautures of the Langmuir isotherm. This separation factor RL is used to predict affinity between the sorbate and sorbent in the biosorption system.lt also indicates whether the adsorption system is favourable or unfavourable (Ngah and Musa, 1998).The separation factor ie RL can be represented as follows
where Cf is the final concentration of metal ion and b is the Langmuir constant.The characteristics of the RL value indicates the nature of biosorption as unfavourable (RL > 1), linear (RL = 1), favourable (0 < RL < 1), and irreversible (RL = 0). With the help of results of the Langmuir studies, it was well observed that, in all selected concentrations (50-1000 mg/I) of metal ions, the separation factor (RL ) was found to be less than l. From the observed RL (RL= Otol) values it was concluded that the cellulose g acrylonitrile copolymer was found to be the favourable adsorbent E.
300
Ceq (mg/dm3)
LangJTIuir constants KL(dm3/g) b(dm3/mg)
Freundlich adsorption isotherm
There is a defined distribution of the solute between the liquid and the solid phases at equilibrium , which can generally be expressed by one or more isotherms (Findon et aI., 1993). The Freundlich expression is an empirical equation based on a heterogeneous surface. The general form of Freundlich equation is
qe
=
K f Ce
lin
(5)
The linearized form of freundlich model was given below
�
g 4.5
log qe log Kf + lin log Ce (6) A plot of log Ce Vs log qe gives a straight line with the slope (lin) and intercept (log Kf) respectively (Figure-6 and Figure-7). With the help of slope and intercept the n and the Kf values were calculated. The observed values of the Kf and n value for both copper (II) and Nickel (II) ions was presented in the table-2. From the observed R2 values and the other datas it was concluded that the Freundlich isotherm model is well fitted for the two metal ions when compared to the Langmuir model. =
o
4.0+------r---. o 100 200 300 400 Ceq (mg/dm3)
Figure (5)-Langmuir isotherm for Ni (II) ion removal on Cellulose-g Acrylonitrile copolymer
TABLE-I
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� Proceedings of the
"International Conference on AdvancedNanomalerials & Emerging Engineering Technologies" (ICANMEET
.� ,--,...._t.:J . _ . 20J3) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, lndia, 24ht
model.Using the Lagergren kinetic model the kinetics of the biosorption of Cu (II) and Ni (II) ions was studied. The biosorption data presented in Figure-(8) were fitted with the following pseudo-first-order rate equation
Copper(lI)
2.0
G.
1.5
�
Cl
.3
Pseudo first order equation
log (qe - qt) log qe - (kI/2.303)t (7) where qe and qt refer to the amount of metal ions adsorbed per unit weight of cellulose graft acrylonitrile copolymer at equilibrium and at any time t. =
1.0 0.5
2.5
O.OI+---r-----r---., 2.0 1.0 0.5 2.5 3.0 1.5
Nickel(lI)
2.0
0.5
1.5
O.O+--"""T"--r----, 300 400 o 200 100
(\)
C) o ...J
Nickel
';"'1.5
Figure (6)-Freundlich isotherm for Cu(Il) biosorption
>-
... Copper +
2.0
Log Ce
1.0
Time in minutes 0.5
Figure-(8)-Pseudo first order kinetic plot for Cu2+ and NiH
The plots of log (qe - qt ) versus t were straight lines. The correlation coefficients (R2 ) which was calculated for the removal of Cu (II) and Ni (II) ion were 0.9843 and 0.9783 respectively. The slopes and intercepts of plots of log (qe - qt) versus t were used to determine the first-order rate constant (k1) and equilibrium adsorption density qe.
O.O,+----r---r----, 1.0 2.5 3.0 1.5 2.0
Log Ce Figure (7)-Freundlich isotherm For Ni (II) biosorption. TABLE-2
Metal ions
Cu(II) Ni(II)
H
Freundlich constants Kr 0.6758 0.2679
n
R2
1.1992
0.9956
1.0560
Pseudo second order
Using the pseudo-second-order equation also, the adsorption process may be described (Ho et al.,1999).The differential equation is the following
dq/dt = k(qe-qt)2
(8)
Integrating the above equation and applying the boundary conditions gives
0.9973
l/qe-qt =l/qe +kt The values of the LangmUIr constants and Freundlich costants of both copper (II) and Nickel(lI) was represented in the table-3. A comparison between Langmuir and Freundlich isotherm models was made. From the 2 comparison of the obtained R values it was concluded that the Freundlich model better describes the adsorption process very effectively when compared to the Langmuir model. F
_26th, July, 2013.
Biosorption kinetics
An investigation was done about the controlling mechanism of adsorption processes such as mass transfer and chemical reaction using the suitable kinetic
(9)
On rearranging the equation (9) we get a linear form (Sag 2002, Wu et aI., 2000).It can be represented as follows
t ----
qt
1
t
=-------1r -----
h
qe
where h k2 qe2 (mg g-lmin-l) which can be regarded as the initial adsorption rate as t tends to 0 and k2 is the rate constant of second order adsorption (g mg-l min-I). The straight line plots of tlqt against t have been tested to obtain rate parameters and it suggests the applicability of this kinetic model to fit the experimental data (Figure-(9».
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� Proceedings of the
"International Conference on AdvancedNanomalerials & Emerging Engineering Technologies" (ICANMEET
.� ,--,...._t.:J . _ . 20J3) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, lndia, 24th _26th, July, 2013.
TABLE 3: COMPARISON OF LANGMUIR AND FREUNDLICH ISOTHERM PARAMETERS Freundlich constants
Langmuir constants
Metal ions
KL
b
L
KF (dmj/g)
n 3 (dm /mg)
L
Cmax
R
0.004873
498.26
0.6426
0.6758
1.1992
0.9956
0.002478
1769.98
0.6088
0.2679
1.0560
0.9973
3 (dm /g)
3 (dm /mg)
Cu(lI)
2.428
Ni(II)
4.386
(mg/g)
R
TABLE 4 Metal
Experiment
Pseudo-first-order kinetic model
IOn
qe (mg/g)
qe (mg/g)
k2 (g mgI min- )
RL
0.9843
168
118.88
0.004492
0.9903
0.9783
140
326.79
0.003568
0.9869
qe (mg/g)
kJ (min-I)
RL
Cu(II)
555.97
0.004011
Ni (II)
558.150
0.004153
3
Pseudo-second-order kinetic model
al value
contact time, and pH had a marked effect on the removal of Cu (II) and Ni (II) ions from metal solution. From the kinetic studies, it was observed that adsorption of Cu2+ and Ni2+was very rapid in the initial stage and decreases while approaching equilibrium. Experimental results are in good agreement with Freundlich adsorption isotherm models, which have shown a good fitting to the experimental data. Adsorption of both Cu 2+ and Ni 2+ obeys pseudo-second order equation with good correlation. From the observed results it was concluded that the cellulose-graft acrylonitrile was found to be an effective adsorbent for the removal of Cu2+ and Ni2+ from aqueous solutions.
..... Copper ... Nickel
2 -
g
o+-----�--�----� 200 o 100 300 400 Time in minutes
REFERENCES
Figure-(9)-Pseudo second order kinetic plot for Cu2+ and Ni2+ Table-4 lists the computed results obtained from both the first order and second-order kinetic model. The correlation coefficients for the second-order kinetic model obtained were greater than 0.98 when compared to the pseudo first order. The calculated qe values also agree well with the experimental data.These indicate that the adsorption system studied belongs to the pseudo-second order(Senthil kumar et aI., 2009) IV. CONCLUSION The graft copolymerisation of acrylonitrile onto the cellulose extracted from the sisal fiber was carried out using ceric ammonium nitate as an initiator.The results of the adsorption studies showed that the adsorbent dose,
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[I] Abdel-Ghani.N.T ,EI-NashaLRM and EI-Chaghaby.G.A (2008) "Removal of Cr (III) and Pb (II) from solution by adsorption onto casuarina glauca tree leaves", EI-Chaghaby et aL EJEAFChe, 7 (7),pp-3 126-3I33. [2] Ajmal, M., Khan, A. H., Ahmad, S., and Ahmad, A.(l998) Water Res. 32(10), 3085 [3] AI-Omair, MA and EI-Sharkawy, EA (2007). "Removal of heavy metals viaadsorption on activated carbon synthesized from solid wastes", Environmental Technology, 28(4), 443-451. [4] Bascil, N., Kocadagistan, E and Kocadagistan, B.(2004) Desalination. 164, 135. [5] Bewley, R. J. F., (1980) "Effect of Heavy Metal Pollution on Oak Leaf Microorganism", App. Enviro. MicrobioL, 40, pp.l053-1059. [6] Carson, B.L, H.V. Ellis, and JL McCann.(l986) "Toxicology and Biological Monitoring of Metals in Humans" , Lewis Publishers, Chelsea, Michigan, p.65, 71, 97, 133,165, 297. [7] Chojnacka, K., Chojnacka A and Gorecka, H. Chemosphere 59, 75 (2005) [8] Crist, RH.; Martin, JR.; Chanko, J.; Crist, D.R.(l996) " Uptake of metals on peatmoss: an ion-exchange process", Environ. Sci. Technol, 30, 2456.
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� Proceedings of the
"International Conference on AdvancedNanomaterials & Emerging Engineering Technologies" (ICANMEET
.� ,--...._-= . ....", 2013) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th _26th, July, 2013. [9] [10] [II]
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