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IOSR Journal of Pharmacy
  Vol. 2, Issue 3, May-June, 2012, PP.579-592



    PROCESS OPTIMIZATION AND BIOSORPTION OF LEAD USING
                ALBIZIA SAMAN LEAF POWDER
          Rao, P.J1, Kumari, R.S1,Babji J.S2, Naga Lakshmi, N.V.R3 and Raju, Ch.A.I.1*
                       1
                        Department of Chemical Engineering, Andhra University, Visakhapatnam – 530 003
           2
               Department of Computer Science and Systems Engineering, Andhra University, Visakhapatnam – 530 003
                      3
                        Department of Petroleum Engineering, GIET College of Engineering, Rajahmundry
ABSTRACT
Water pollution is one of the signs that humans have exceeded the limits and causing health problems for living beings on
earth. The present paper comprises the optimization and biosorption of lead from aqueous solution using Albizia saman leaf
powder as biosorbent. Single Step Optimization was considered for preliminary runs with the variables agitation time,
biosorbent size, pH of the solution, initial concentration of the aqueous solution, dosage of biosorbent and temperature. The
Central Composite Design (CCD) was used for final runs optimization using Response Surface Methodology (RSM). Results
indicated that the optimum agitation time for biosorption of lead is 50 min. The increase in mass of biosorbent lead to
increase in lead (pb) ion biosorption due to the increase in the number of active biosorption sites. Maximum percentage
biosorption is observed at a pH of 6 and with particle size of 53 µm. Experimental data were better described by pseudo-
second-order model. The adsorption isotherm could be well fitted by the Langmuir equation followed by Freundlich and
Temkin. Over and all, Albizia Saman leaf powder can be used as an effective natural biosorbent for the economic treatment
of aqueous solutions containing lead.

Keywords - Albizia Saman, biosorption, optimization, isotherms, kinetics

1. INTRODUCTION
          Because of its relative recent development in the planet's history, pollution is a human problem. Before the 19th
century Industrial Revolution, people lived more in harmony with their immediate environment. If one or more substances
have built up in resources like water, air etc., to such an extent that they cause problems for living beings, we treat it as
polluted one. As industrialization has spread around the globe, the problem of pollution spread along with it. Intensive
mining operations and processing of minerals to meet the increasing needs of our society have led to environmental pollution
in specific locations all over the world [1]. Heavy metals are discharged from various industries such as electroplating, plastic
manufacturing, textile, storage batteries, mining and metallurgical process [2]. Water pollution of toxic heavy metal ions
discharged from the industries and inhabited areas is seriously harmful to the health of human beings and the eco-system.
Among these heavy metals, lead may be the severe pollutant sources due to its wide applications in industries, which may
produce wastewater containing lead at the concentrations higher than the recommended doses of 0.015 mg/L.
Microorganisms immobilized on natural and synthetic adsorbents have been used for separation and preconcentration of
heavy metals at trace levels [3, 4, 5, 6, 7]. Most studies have focused on the removal of Pb2+, Cd2+, and Ni2+ from wastewater
by using various biosorbents [8]. Biosorbents are prepared from the naturally abundant or waste biomass of algae, moss,
fungi or bacteria [9]. Hence the naturally and abundantly available albizia saman has been selected for the present study for
the removal of lead from aqueous solutions.

2. MATERIALS AND METHODS
2.1 Biosorbent Preparation
          Albizia saman leaves were obtained from Rajahmundry. The leaves are washed thrice with tap water and once with
distilled water in order to remove adhering mud, impurities etc. It was dried in sunlight for one week until all the moisture
was evaporated. The crispy powder were then crushed and grinded to powder, separated using British Standard Sieves (BSS)
and stored in dry vacuum packs to prevent moisture content and readily used as biosorbent.
2.2 Batch sorption studies
          Preliminary experiments were conducted in 250 ml Erlenmayer flasks containing 50 ml of 20 mg/L metal solution
using single step optimization procedure. The flasks were agitated on an orbital shaker at 180 rpm and samples were taken at
predetermined time intervals (1, 3, 5, 10, 15, 20, 25, 30, 40, 50, 60, 90, 120, 150 & 180 min) & centrifuged at 14000 rpm and
the supernatant liquid was analysed in Atomic Absorption Spectrophotometer (AAS) for final concentrations. Similarly the
other variables were varied in a wide range: Biosorbent Size (53, 75, 104, 125 & 152 µm), pH of the aqueous solution (2, 3,
4, 5, 6, 7 and 8), Initial concentration of lead solution (25, 30, 60, 120 & 180 mg/L), Biosorbent Dosage (10, 20, 30, 40, 50 &
60 g/L) and Temperature (283, 293, 303, 313 & 323 K).
2.3 Process optimization


    ISSN: 2250-3013                                        www.iosrphr.org                                        579 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592


         Final experimental runs for optimization were obtained through Response Surface Methodology from Design of
Experiments (DoE) using STATISTICA software. The extent of biosorption of lead calculated at the preliminary optimum
conditions is verified with the final runs for the optimum conditions.

3. RESULTS AND DISCUSSION
          The potential of dry Albizia saman leaf powder as a biosorbent for the biosorption of lead metal present in an
aqueous solution is investigated in the present investigation. The effects of various parameters on biosorption of lead are
studied. The numerical analysis of the investigation was undertaken applying CCD using RSM.
3.1 Effect of agitation time
          The equilibrium agitation time is determined by plotting the % biosorption of lead against agitation time as shown in
fig. 1. For 0.5g (10 mg/L) of biosorbent and 53μm of biosorbent size in the interaction time intervals of 1 to180 min 58.30 %
(1.166 mg/g) of lead is biosorbed in the first 1 min. The % biosorptionis increased briskly up to 50 min reaching 79.45 %
(1.589 mg/g). Beyond 50 min, the % biosorption is constant indicating the attainment of equilibrium conditions. The
maximum biosorption of 79.45% (1.589 mg/g ) is attained for 50 min of agitation time with 10 g/L of 53 μm size biosorbent
mixed in 50 mL of aqueous solution (C0=20 mg/L) [10, 11].
3.2 Effect of biosorbent size
          The percentage biosorption is increased from 72.12 (1.4424 mg/g) to 79.45 % (1.589 mg/g) as the biosorbent size
decreases from 152 to 53 μm presented in fig. 2. This phenomenon is expected, as the size of the particle decreases, surface
area of the biosorbent increases; thereby the numbers of active sites on the biosorbent are better exposed to the biosorbate.
3.3 Effect of pH of the aqueous solution
          In order to determine the optimal value, pH of the aqueous solution is varied from 2 to 8. The pH of aqueous
solution is shown against % biosorption of lead in fig 3. The % biosorption of metal is increased from 58.42 % (1.1684 mg/g)
to 77.18 % (1.5436 mg/g) as pH is increased from 2 to 6 and decreased beyond pH value of 7. The predominant sorbing
forms of lead are Pb2+ and PbOH+ that occurr in the pH range of 4–6. This is the reason for higher biosorption of lead in the
pH range of 4–6. At pH higher than 6, precipitation of lead occurred and biosorption due to biosorption is reduced [12, 13,
14].
3.4 Effect of initial concentration of lead in the aqueous solution
          The effect of initial Pb2+ ion concentration is investigated in the range of 20-180 mg/L. The effect of initial
concentration of lead in the aqueous solution on the percentage biosorption of lead is shown in fig. 4. The percentage
biosorption of lead is decreased from 77.12% to 58.68% with an increase in C0 from 20 mg/L to 180 mg/L while the uptake
capacity is increased from 1.5424 to 10.5624 mg/g [15].
 3.5 Effect of biosorbent dosage
          The biosorption of lead increases from 77.14% (1.5428 mg/g) to 83.78 % (0.5585 mg/g) with an increase in
biosorbent dosage from 10 to 30 g/L, shown in fig. 5. Such behavior is obvious because with an increase in biosorbent
dosage, the number of active sites available for lead biosorption would be more. The change in percentage biosorption of lead
is marginal from 83.78% (0.5585 mg/g) to 84.92% (0.2830 mg/g) when ‘w’ is increased from 30 to 60 g/L. Hence all other
experiments are conducted at 30 g/L dosage.
3.6 Effect of temperature
          The effect of temperature on the equilibrium metal uptake was significant. The effect of changes in the temperature
on the lead uptake is shown in fig. 6. When temperature was lower than 303 K, Lead uptake increased with increasing
temperature, but when temperature was over 303 K, the results slowed down and the increase is marginal. This response
suggested a different interaction between the ligands on the cell wall and the metal. Below 303 K, chemical biosorption
mechanisms played a dominant role in the whole biosorption process, biosorption was expected to increase by increase in the
temperature. While at higher temperature, the plant powder was in a nonliving state, and physical biosorption became the
main process. Physical biosorption reactions were normally exothermic, thus the extent of biosorption generally is constant
with further increasing temperature [16].




 ISSN: 2250-3013                                        www.iosrphr.org                                       580 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



3.7 Isotherms
3.7.1 Langmuir isotherm
           Irving Langmuir developed an isotherm named as Langmuir isotherm, which is the most widely used simple two-
parameter equation. Langmuir isotherm is drawn between Ce vs Ce/ qe shown in fig 7. The equation obtained is (Ce/qe) =
2.8729 Ce + 0.05929 with a good linearity (correlation coefficient, R2=0.9791) indicating strong binding of lead ions to the
surface of albizia saman leaf powder. The separation factor (RL) of 0.9219 shows favorable biosorption (0< RL<1). Hence a
maximum biosorption capacity of the Albizia saman leaf powder for lead is find to be 16.8656 mg/g by Langmuir isotherms
at 303K (mass of biosorbent: 10 g/L) [17, 18].
3.7.2 Freundlich isotherm
           Freundlich empirical adsorption isotherm equation can be applied in case of low and intermediate concentration
ranges. Freundlich isotherm is drawn between log qe and log Ce, in fig. 8 The equation obtained is log qe = 0.6815 log Ce –
0.2404. The resulting equation has a correlation coefficient of 0.9655. The ‘n’ value in the above equations is 0.6815,
satisfies the condition of 0<n<1 indicating favorable biosorption. Kf is 0.5748 mg/g [19].
3.7.3 Temkin isotherm
           Temkin and Pyzhev isotherm equation describes the behavior of many adsorption systems on the heterogeneous
surface. The present data are analysed according to the linear form of Temkin isotherm and the linear plot is shown in fig. 9
The equation obtained for lead biosorption is: q e = 3.1546 ln Ce -3.8813 with a correlation coefficient 0.9637. The best fit
model is determined based on the linear regression correlation coefficient (R2) [20].
3.8 Kinetics of biosorption
           Kinetic models are used to describe the order of biosorbate – biosorbent interactions. Traditionally, the first order
model of Lagergren finds wide application. In the case of biosorption preceded by diffusion through a boundary, the kinetics
in most cases follows the first order rate equation of Lagergren [21]:
(dqt/dt) = K1 (qe – qt)
where qe and qt are the amounts adsorbed at t, min and equilibrium time and Kad is the rate constant of the first order
adsorption.
The above equation can be presented as
log (qe – qt) = log qe – (K1/2.303) t
log (qe – qt) = –0.02357 t – 0.3027 ; R2 = 0.9620
Plot of log (qe–qt) versus ‘t’ gives a straight line for first order kinetics, facilitating the computation of biosorption rate
constant (K1). If the experimental results do not follow the above equation, they differ in two important aspects:
K1 (qe – qt) does not represent the number of available adsorption sites and log q e is not equal to the intercept.
In such cases, pseudo second order kinetic equation [22, 23]:
(dqt/dt ) = K2 (qe – qt)2 is applicable, where ‘K2’ is the second order rate constant.
The other form of the above equation is:
(t/qt) = (1/ K2qe2) + (1/qe) t
(t/qt) = 0.6229 t + 1.1720; R2 = 0.9959
The pseudo second order model based on above equation, considers the rate-limiting step as the formation of chemisorptive
bond involving sharing or exchange of electrons between the biosorbate and biosorbent. If the pseudo second order kinetics is
applicable, the plot of (t/qt) versus ‘t’ gives a linear relationship that allows computation of q e and K2.
In the present study, the kinetics are investigated with 50 mL of aqueous solution (C 0= 20 mg/L) at 303 K with the interaction
time intervals of 1 min to 50 min. Lagergren and pseudo plots for biosorption of lead with biosorbent size 53 μm of Albizia
saman leaf powder are drawn in figs. 10 & 11. As the correlation coefficient values for the pseudo second order kinetics is
0.99 which is better than first order kinetics (R2=0.962), very well describes the biosorption mechanism of lead using Albizia
saman leaf powder.
3.9 Thermodynamics of biosorption
           The process of Biosorption is temperature dependant. In general, the temperature dependence is associated with
three thermodynamic parameters namely change in enthalpy of biosorption (∆H), change in entropy of biosorption (∆S) and
change in Gibbs free energy (∆G).
The Van’t Hoff’s plots for the biosorption data obtained at initial concentrations of the lead are shown in fig. 12. The
equation obtained is log qe / Ce = –0.41701(1/T) + 0.5921. The correlation coefficient is 0.9568. In the present study, the
enthalpy change is ∆H is 7.9845 J/mole is positive indicating that the biosorption is endothermic. The value of ∆S is 11.3370
J/mole is also positive indicating the irreversibility of process, ∆G is 3427.1334 J/mole is negative indicating the spontaneity
of biosorption.



 ISSN: 2250-3013                                        www.iosrphr.org                                        581 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



3.10 Optimization of the selected parameters using CCD
          In order to determine an optimum condition for lead ions removal, the parameters having greater influence over the
response are to be identified. In the present study, the relationship between four independent variables and percent of lead
ions biosorption is fitted well with the quadratic model. The regression equation for the optimization of lead biosorption: %
biosorption of lead (Y) is a function of the W (X1), Co (X2), pH (X3), and T (X4). Table–1 presents the coded levels and Table–
2 represents the variations in the corresponding coded values of four parameters and response based on experimental runs and
predicted values proposed by CCD design.
Y = –452.007 + 0.429 X1 + 0.369 X2 + 5.846 X3 + 3.347 X4 – 0.006X12 – 0.015X22 – 0.548 X32 – 0.006 X42 + 0.004 X1X2 –
0.010 X1X3 + 0.026 X2X3 + 0.002 X3X4            -------------------------------- (1)
Interpretation of the regression analysis:
          The results of above regression model for Eq. (1) (in the form of analysis of variance ANOVA) are compiled in
Table-3. In general, the Fischer’s ‘F-statistics’ value (=MSmodel/MSerror), where MS (mean square) with a low probability ‘P’
value indicates high significance of the regression model. The ANOVA of the regression model demonstrates that the model
is highly significant, as is evident from the Fisher’s F-test (Fmodel = 33852) and a very low probability value (Pmodel >
F=0.000000). More over, the computed F-value (F0.05 (14.15) = MSmodel/MSerror = 33852) is greater than that of the tabular F-
value (F0.05 (14.15) tabulars = 2.42) at the 5% level, indicating that the treatment differences are significant.
The significance of the regression coefficient of the parameter can be verified by the Student’s t-test as a tool, while ‘P’
values signify the pattern of interaction among the factors. From the Table–4, we can observe that, the larger the value of t
and smaller the value of P, more significant is the corresponding coefficient term. By analyzing the ‘t’ values and ‘P’ values
from Table-4, it is found that the X1, X2, X3, X4, X12 , X22 , X32 , X42 X1X2, X1X3, X1X4, X2X3, X2X4, X3X4 have high significance
to explain the individual and interaction effect of biosorption variables on the biosorption of lead to predict the response.
          A positive sign of the coefficient represents a synergistic effect which means response (% biosorption of lead
increases with the increase in effect, while a negative sign indicates an antagonistic effect which means response (%
biosorption of lead) decreases with the increase in effect. The optimal set of conditions for maximum percentage biosorption
of lead is pH = 6.0250, biosorption dosage (w) = 31.7191 g/L, initial lead concentration (C o) = 19.8996 mg/L and
temperature = 304.0673 K. The extent of biosorption of lead calculated at these optimum conditions is 84.90612%. Fig. 13
shows the comparison between the % biosorption obtained through experiments and predicted. The correlation coefficient
(R2) provides a measure of the models variability in the observed response values. The closer the R2 value to 1, the stronger
the model is and it predicts the response better. In the present study the value of the regression coefficient (R 2 = 0.99997)
indicates that 0.003% of the total variations are not satisfactorily explained by the model. The ANOVA Table-3 can be used
to test the statistical significance of the ratio of mean square due to regression and mean square due to residual error.
Figs. 15 to 20 were represented as a function of two factors at a time, holding other factors fixed at zero level for the
Interaction effects of biosorption variables.




 ISSN: 2250-3013                                         www.iosrphr.org                                         582 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



4. FIGURES AND TABLES

                                                         85

                                                                                                                 biosorbent=albizia saman leaf power
                                                         80




                                  %biosorption of lead
                                                         75                                                                                                  Dp=53m
                                                                                                                                                             w=10g/L
                                                                                                                                                             T=303K
                                                         70                                                                                                  C0=20mg/L
                                                                                                                                                             pH=6.8


                                                         65

                                                                                                                                                    % biosorption of lead
                                                         60



                                                         55
                                                                                         0              20       40        60       80      100      120     140      160       180        200

                                                                                                                                  agitation time, t min


                                  Fig. 1 Effect of agitation time on % biosorption of lead


                                                                                                  90                                                                                            1.60

                                                                                                  88                    Biosorbent = Albizia saman leaf power                                   1.58

                                                                                                  86
                                                                                                                                                                                                1.56
                                                                                                                                                                      W=10g/L
                                                                                                                                                                      T= 303K
                                                                          % biosorption of lead




                                                                                                  84
                                                                                                                                                                      pH= 6.8                   1.54
                                                                                                                                                                      t =50min




                                                                                                                                                                                                                  metal uptake
                                                                                                  82                                                                  C0=20mg/L
                                                                                                                                                                                                1.52
                                                                                                  80
                                                                                                                                                                                                1.50
                                                                                                  78
                                                                                                                                                                                                1.48
                                                                                                  76
                                                                                                                                                                                                1.46
                                                                                                  74
                                                                                                                        % biosorption
                                                                                                  72                    metal uptake                                                            1.44

                                                                                                  70                                                                                            1.42
                                                                                                       40         60              80          100           120         140               160

                                                                                                                                       Biosorbent size m


                              Fig. 2 Variations in % biosorption of lead using biosorbent sizes


                                                                                              80                                                                                           2.0

                                                                                                       Biosorbent= Albizia saman leaf power

                                                                                              75                                                                                           1.8
                                                                                                                  % biosorption
                                                         % biosorption of lead




                                                                                                                  metal uptake
                                                                                                                                                                                                   metal uptake




                                                                                              70                                                                                           1.6




                                                                                              65                                                                                           1.4
                                                                                                                                                    Dp=53m
                                                                                                                                                    T=303K
                                                                                                                                                    W=10 g/L
                                                                                                                                                    t = 50min
                                                                                              60                                                                                           1.2
                                                                                                                                                    C0=20 mg/L



                                                                                              55                                                                                           1.0
                                                                                                   1         2         3           4         5         6          7         8         9

                                                                                                                                pH of aqueous solution



                                                                                                   Fig. 3 Effect of pH on % biosorption of lead




 ISSN: 2250-3013                                                                                                           www.iosrphr.org                                                                                       583 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



                                                                                                            80                                                                                              12

                                                                                                                             Biosorbent= Albizia saman leaf power
                                                                                                                                                                                                            10
                                                                                                            75
                                                                                                                                                        % biosorption
                                                                                                                                                        metal uptake




                                                                                    % biosorption of lead
                                                                                                                                                                                                            8




                                                                                                                                                                                                                           metal uptake
                                                                                                            70

                                                                                                                                                                                                            6

                                                                                                            65
                                                                                                                                                                                                            4
                                                                                                                                                  Dp=53m
                                                                                                                                                  T=303K
                                                                                                            60                                    pH= 6
                                                                                                                                                                                                            2
                                                                                                                                                  W=10g/L
                                                                                                                                                  t =50min

                                                                                                            55                                                                                             0
                                                                                                                  0    20       40         60      80      100      120         140     160   180       200

                                                                                                                              initial concentration of aqueous solution, mg/L


                              Fig. 4 Effect of initial concentration for the biosorption of lead


                                                                                                    86                                                                                                1.8
                                                                                                                  Biosorbent =Albizia saman leaf power
                                                                                                                                                                                                      1.6
                                                                                                    84
                                                                                                                                                                                                      1.4
                                                                                                                                                                        % biosorption
                                                            % Biosorption of lead




                                                                                                                                                                        metal uptake
                                                                                                                                                                                                      1.2




                                                                                                                                                                                                            Metal uptake
                                                                                                    82
                                                                                                                                                                   Dp=53m
                                                                                                                                                                                                      1.0
                                                                                                                                                                   T=303K
                                                                                                    80                                                             pH=6
                                                                                                                                                                   C0=20mg/L                          0.8
                                                                                                                                                                   t=50min
                                                                                                                                                                                                      0.6
                                                                                                    78
                                                                                                                                                                                                      0.4


                                                                                                    76                                                                                                0.2
                                                                                                            0.0        0.5           1.0          1.5        2.0          2.5          3.0      3.5

                                                                                                                                       Biosorbent dosage, W, g/L



                                Fig. 5 Effect of biosorbent dosage on % biosorption of lead


                                                                           86
                                                                                                             Biosorbent = Albizia saman leaf powder
                                                                           85                                                                                                                       0.58

                                                                                                                      % biosorption
                                                                           84                                         metal uptake
                                    % biosorption of lead




                                                                                                                                                                                                    0.56
                                                                           83
                                                                                                                                                                                                            metal uptake




                                                                           82                                                                            Dp=53m
                                                                                                                                                         pH=6                                       0.54
                                                                                                                                                         C0=20 mg/L
                                                                           81
                                                                                                                                                         W=30 g/L
                                                                                                                                                         t=50min
                                                                           80
                                                                                                                                                                                                    0.52

                                                                           79


                                                                           78                                                                                                                     0.50
                                                                                                   280                  290                 300              310                 320           330

                                                                                                                                            Temperature, K



                                  Fig. 6 Effect of temperature for the biosorption of lead




ISSN: 2250-3013                                                                                                                      www.iosrphr.org                                                                                      584 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



                                                8

                                                              Biosorbent = Albizia saman leaf power
                                                7

                                                                                                                          91
                                                                                                                       .97
                                                                                                                 2   =0
                                                6                                                         ,r
                                                                                                        92
                                                                                                      92
                                                                                                   .05




                                  Ce/qe gm/L
                                                                                                 +0
                                                                                       C        e
                                                                                    29
                                                5                                .87
                                                                               =2
                                                                         /q   e                                                        Dp= 53 m
                                                                    C   e
                                                                                                                                       W = 10 g/L
                                                4                                                                                      T =303 K
                                                                                                                                       pH =6.0
                                                                                                                                       t = 50min

                                                3



                                                2
                                                     0       10               20                30               40             50            60           70          80

                                                                                                                 Ce

                                                         Fig. 7 Langmuir isotherm for biosorption of lead


                                               1.2
                                                             Biosorbent = Albizia saman leaf power
                                               1.0

                                                                                                                                55
                                                                                                                             .96
                                               0.8                                                                     2   =0
                                                                                                                ,r
                                                                                                              04
                                                                                                            24
                                                                                                        -0.
                                                                                               Ce
                                  log qe




                                                                                            log
                                               0.6                                        15
                                                                                       .68
                                                                                     =0                                              Dp= 53 m
                                                                                 q   e
                                                                              log
                                                                                                                                     W = 10 g/L
                                               0.4                                                                                   T =303 K
                                                                                                                                     pH =6.0
                                                                                                                                     t = 50min
                                               0.2



                                               0.0
                                                     0.4      0.6             0.8               1.0          1.2              1.4          1.6           1.8     2.0

                                                                                                            log Ce

                                                     Fig. 8 Freundlich isotherm for biosorption of lead



                                               -2


                                                             Biosorbent = Albizia saman leaf power
                                               0
                                                                                     q
                                                                                         e =3
                                                                                            .15
                                                                                               46
                                               2                                                      lnC
                                                                                                        e- -3
                                                                                                             .88
                                                                                                                13
                                                                                                                  ,r2                      Dp= 53 m
                                                                                                                    =0
                                                                                                                      .96
                                  qe




                                               4                                                                         37                W = 10 g/L
                                                                                                                                           T =303 K
                                                                                                                                           pH =6.0
                                                                                                                                           t = 50min
                                               6



                                               8



                                               10
                                                    1.0       1.5              2.0                2.5                 3.0            3.5           4.0          4.5

                                                                                                        ln Ce

                                                     Fig. 9 Temkin isotherm for biosorption of lead




ISSN: 2250-3013                                                                     www.iosrphr.org                                                                         585 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



                                                  -1.4
                                                                            Biosorbent = Albizia saman leaf power
                                                  -1.2
                                                                                                                                         20
                                                                                                                                      .96
                                                                                                                                2   =0
                                                                                                                             ,r
                                                                                                                           27
                                                  -1.0                                                                  .30
                                                                                                                 7   t-0
                                                                                                              35
                                                                                                           02
                                                                                                       -0.
                                                                                           )=




                                    log (qe-qt)
                                                  -0.8
                                                                                        -q t
                                                                                    (q e
                                                                                log                                                             Dp= 53 m
                                                  -0.6
                                                                                                                                                W = 10 g/L
                                                                                                                                                T =303 K
                                                                                                                                                pH =6.0
                                                  -0.4                                                                                          C0=20 mg/L


                                                  -0.2


                                                   0.0
                                                                        0                   10                        20                  30                     40            50

                                                                                                                     t, min

                                                      Fig. 10 First order kinetics for biosorption of lead



                                                   35

                                                                 Biosorbent = Albizia saman leaf power
                                                   30


                                                   25
                                                                                                                   59
                                                                                                            2 0.
                                                                                                                 99
                                                   20                                                       r=
                                                                                                   0,
                                                                                                 72
                                                                                            t+1.1
                                       t/qt




                                                   15                                   9                                              Dp= 53 m
                                                                                     22
                                                                                =0.6
                                                                                                                                       W = 10 g/L
                                                                            t/q t                                                      T =303 K
                                                   10
                                                                                                                                       pH =6.0
                                                                                                                                       C0=20 mg/L
                                                     5


                                                     0



                                                                    0                10                     20                 30                40                   50       60

                                                                                                                     t, min

                                                     Fig. 11 Second order Kinetics for biosorption of lead



                                                  -0.65

                                                                                            Biosorbent = Albizia saman leaf power
                                                  -0.70
                                                                                                                 log
                                                                                                                       q/
                                                                                                                       e C
                                                                                                                              e =-0
                                                  -0.75                                                                             .41
                                                                                                                                       70
                                                                                                                                          (1  / t)
                                                                                                                                                  +0
                                  logqe/Ce




                                                                                                                                                    .59
                                                                                                                                                          21
                                                  -0.80                                                                                                      ,   r2
                                                                     Dp= 53 m                                                                                    =0.9
                                                                                                                                                                        56
                                                                     W = 10 g/L                                                                                            8
                                                                     t =50 min
                                                  -0.85              pH =6.0
                                                                     C0=20 mg/L0=20 mg/L

                                                  -0.90



                                                  -0.95
                                                          3.0           3.1                      3.2                   3.3                3.4                     3.5          3.6

                                                                                                             1/t x 103min

                                                                Fig. 12 Vant Hoff’s plot for biosorption of lead




ISSN: 2250-3013                                                                       www.iosrphr.org                                                                                586 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592




                                               Fig. 13 Predicted vs Observed




                                                   Fig. 14 Pareto Chart




                                  Fig. 15 Surface contour plot for the effects of dosage and
                                      initial concentration of lead on % biosorption




ISSN: 2250-3013                                       www.iosrphr.org                          587 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592




                                      Fig. 16 Surface contour plot for the effects of dosage
                                               and pH on % biosorption of lead




                                     Fig. 17 Surface contour plot for the effects of dosage &
                                            Temperature on % biosorption of lead




                                Fig. 18 Surface contour plot for the effects of initial concentration
                                                 and pH on % biosorption of lead




ISSN: 2250-3013                                         www.iosrphr.org                                 588 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592




                               Fig. 19 Surface contour plot for the effects of initial concentration
                                            and Temperature on % biosorption of lead




                                   Fig. 20 Surface contour plot for the effects of pH and
                                          Temperature on % biosorption of lead




                                                                TABLE–1
                                  Levels of different process variables in coded and un-coded form for
                                         % biosorption of lead using Albizia saman leaf powder

                                          Var          Name                    Range and levels

                                                                         -2    -1     0      1    2

                                          X1     Biosorbent dosage,      10    20    30     40    50
                                                       w, g/L

                                          X2    Initial concentration,   10    15    20     25    30
                                                       Co, mg/L

                                          X3       pH of aqueous          4     5     6      7    8
                                                     solution
                                          X4     Temperature, T, K       283   293   303    313   323




ISSN: 2250-3013                                            www.iosrphr.org                               589 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592


                                TABLE–2 Results from CCD for lead biosorption by Albizia saman leaf powder
                                     Runs     X1, W      X2, Co        X3, pH   X4, T       Experimental    Predicted

                                      1       -1.00      -1.00          -1.00   -1.00          82.70          82.70

                                      2       -1.00      -1.00          -1.00    1.00          82.98          82.98

                                      3       -1.00      -1.00          1.00    -1.00          82.72          82.71

                                      4       -1.00      -1.00          1.00     1.00          83.06          83.05

                                      5       -1.00      1.00           -1.00   -1.00          81.94          81.93

                                      6       -1.00      1.00           -1.00    1.00          82.16          82.15

                                      7       -1.00      1.00           1.00    -1.00          82.44          82.44

                                      8       -1.00      1.00           1.00     1.00          82.76          82.75

                                      9       1.00       -1.00          -1.00   -1.00          82.96          82.96

                                      10      1.00       -1.00          -1.00    1.00          83.14          83.13

                                      11      1.00       -1.00          1.00    -1.00          82.54          82.54

                                      12      1.00       -1.00          1.00     1.00          82.80          82.80

                                      13      1.00       1.00           -1.00   -1.00          83.04          83.04

                                      14      1.00       1.00           -1.00    1.00          83.18          83.18

                                      15      1.00       1.00           1.00    -1.00          83.16          83.15

                                      16      1.00       1.00           1.00     1.00          83.36          83.36

                                      17      -1.00      0.00           0.00     0.00          82.04          82.04

                                      18      2.00       0.00           0.00     0.00          82.92          82.91

                                      19      0.00       -2.00          0.00     0.00          83.50          83.49

                                      20      0.00       2.00           0.00     0.00          83.28          83.28

                                      21      0.00       0.00           -2.00    0.00          82.60          82.59

                                      22      0.00       0.00           2.00     0.00          82.78          82.78

                                      23      0.00       0.00           0.00    -2.00          82.44          82.43

                                      24      0.00       0.00           0.00     2.00          82.92          82.92

                                      25      0.00       0.00           0.00     0.00          84.88          84.88

                                      26      0.00       0.00           0.00     0.00          84.88          84.88

                                      27      0.00       0.00           0.00     0.00          84.88          84.88

                                      28      0.00       0.00           0.00     0.00          84.88          84.88

                                      29      0.00       0.00           0.00     0.00          84.88          84.88

                                      30      0.00       0.00           0.00     0.00          84.88          84.88




                                                          Table–3
                                     ANOVA of lead biosorption for entire quadratic model

                                                                                   Mean
                                       Source of variation        SS       df                     F-value   P>F
                                                                                square(MS)



                                             Model           24.3289       14    1.737778        33852.82   0.0000




                                             Error           0.00077       15   0.0000513




                                             Total           24.32967



                                       Df- degree of freedom; SS- sum of squares; F- factor F; P- probability.
                                                           R2=0.99997; R2 (adj):0.99994




ISSN: 2250-3013                                                   www.iosrphr.org                                       590 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592


                                                                               Table–4
                                     Estimated regression coefficients for the lead biosorption onto Albizia saman leaf powder

                                                  Terms           Regression    Standard error of   t-value    P-value
                                                                  coefficient     the coefficient
                                             Mean/Intercept        -452.007         1.335753        -338.391   0.000000
                                            Dosage, w, g/L (L)      0.429           0.005629        76.293     0.000000
                                            Dosage, w, g/L (Q)      -0.006          0.000014        -439.689   0.000000
                                            Conc, Co, mg/L (L)      0.369           0.011310        32.663     0.000000
                                            Conc, Co, mg/L (Q)      -0.015          0.000055        -273.032   0.000000
                                                 pH (L)             5.846           0.057298        102.035    0.000000
                                                 pH (Q)             -0.548          0.001365        -401.230   0.000000
                                          Temperature, T, K (L)     3.347           0.008391        398.867    0.000000
                                          Temperature, T, K (Q)     -0.006          0.000014        -403.061   0.000000
                                                1L by 2L            0.004           0.000036        120.992    0.000000
                                                1L by 3L            -0.010          0.000179        -58.048    0.000000
                                                1L by 4L            -0.000          0.000018        -13.288    0.000000
                                                2L by 3L            0.026           0.000357        72.036     0.000000
                                                2L by 4L            -0.000          0.000036         -6.294    0.000014
                                                3L by 4L            0.002           0.000179        10.491     0.000000




5. CONCLUSION
          Both Preliminary and finals experimental runs are carried out to find out the equilibrium, isotherms, kinetics and
thermodynamic parameters for biosorption of lead from an aqueous solution using Albizia saman leaf powder. The analysis
of the experimental and theoretical data results in the conclusions that the equilibrium agitation time for lead biosorption is
50 minutes. The % biosorption of lead from an aqueous solution increased from 72.12 to 79.45 % with a decrease in the
particle size of the biosorbent from 152 to 53 µm and increases from 77.14 to 83.78 % with increase in biosorbent dosage
from 10 to 30 g/L. With an increase in the initial concentration of lead in the aqueous solution (20 to 180 mg/L), the
percentage biosorption of lead from the aqueous solution is decreased from 77.12 to 58.68 %. Percentage biosorption of lead
from the aqueous solution increased significantly with increase in pH from 2 to 6 (58.42 to 77.18 %). Hereafter, percentage
biosorption decreases for further increase in pH from 6 to 8 (77.18 to 69.42 %). The maximum uptake capacity of 16.8656
mg/g is obtained at a temperature of 303 K. The present study involves the use of statistical experimental design to optimize
process conditions for maximal biosorption of lead from aqueous solution using CCD involving RSM. The maximum
biosorption of lead (84.90612 %) onto Albizia saman leaf powder is observed when the processing parameters are set as
follows: pH = 6.0250, w = 31.7191 g/L, Co = 19.8996 mg/L and T = 304.0673 K. The kinetic studies showed that the
biosorption of lead is better described by pseudo second order kinetics. The thermodynamic data depicted that % biosorption
of lead increased with increase in temperature up to some extent.




 ISSN: 2250-3013                                                      www.iosrphr.org                                            591 | P a g e
IOSR Journal of Pharmacy
Vol. 2, Issue 3, May-June, 2012, PP.579-592



REFERENCES
 [1]          Prerna Ahuja, Rani Gupta, R.K. Saxena, Sorption and Desorption of Cobalt by Oscillatoria anguistissima,
              Current Microbiology Vol. 39, 1999, pp. 49–52
 [2]           Ahmet Çabuk, Tamer Akar, Sibel Tunali, Özge Tabak, Biosorption characteristics of Bacillus sp. ATS-2
              immobilized in silica gel for removal of Pb(II), Journal of Hazardous Materials, Volume 136, Issue 2, 21,
              2005, Pages 317–323
 [3]          Volesky, B., Removal and recovery of heavy metals by biosorption [C] Volesky B, ed. Biosorption of Heavy
              Metals (Boca Raton: CRC Press, 1990) 12–13.
 [4]          Volesky, B, Biosorption of Heavy Metals (CRC Press, Boca Raton 1990).
 [5]          Lo, W., Chua, H., Lam, K.H., Bi, S.P., A comparative in`vestigation on the biosorption of lead by
              filamentous fungal biomass, Chemosphere 39, 1999, 2723–2736.
 [6]          Alaa H. Hawari, Catherine N. Mulligan, Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by
              anaerobic granular biomass, Bioresource Technology 97, 2006, 692–700.
 [7]          Ankit Balaria, Silke Schiewer, Assessment of biosorption mechanism for Pb binding by citrus pectin,
              Separation and Purification Technology 63, 2008, 577–581.
 [8]          Anushree Malik, Metal bioremediation through growing cells, Environment International 30, 2004, 261–
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 [9]          Arzu,Y.and Dursun,A., Comparative study on determination of the equilibrium, kinetic and thermodynamic
              parameters of biosorption of copper (II) and lead (II) ions onto pretreated Aspergillus niger, Biochem.Eng.
              J., 28, 2006, 187-195.
 [10]         Chandrasekhar K, Subramanian S, Modak JM, Natarajan KA, Removal of metals using an industrial
              biomass with reference to environmental control, Int J Miner Process 53, 1998, 107–120.
 [11]         K. Parvathi, R. Nareshkumar R. Nagendran, Biosorption of lead by Aspergillus niger and Saccharomyces
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 [13]         O. Masala, E.J.L. McInnes, P. Obrien, Modelling the formation of granules: the influence of lead ions on
              calcium pyrophosphate precipitates, Inorg, Chim. Acta 339, 2002, 366–372.
 [14]         Goyal N, Jain SC, Banerjee, Comparative studies on the microbial adsorption of heavy metals, Adv Environ
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 [15]         Sag, Y., D. Ozer and T. Kutsal, A comparative study of the biosorption of lead(II) ions to Z. ramigera and R.
              arrhizus, Process Biochem., 30, (2), 1995, 169-174.
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ISSN: 2250-3013                                     www.iosrphr.org                                       592 | P a g e

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IOSRPHR(www.iosrphr.org) IOSR Journal of Pharmacy

  • 1. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 PROCESS OPTIMIZATION AND BIOSORPTION OF LEAD USING ALBIZIA SAMAN LEAF POWDER Rao, P.J1, Kumari, R.S1,Babji J.S2, Naga Lakshmi, N.V.R3 and Raju, Ch.A.I.1* 1 Department of Chemical Engineering, Andhra University, Visakhapatnam – 530 003 2 Department of Computer Science and Systems Engineering, Andhra University, Visakhapatnam – 530 003 3 Department of Petroleum Engineering, GIET College of Engineering, Rajahmundry ABSTRACT Water pollution is one of the signs that humans have exceeded the limits and causing health problems for living beings on earth. The present paper comprises the optimization and biosorption of lead from aqueous solution using Albizia saman leaf powder as biosorbent. Single Step Optimization was considered for preliminary runs with the variables agitation time, biosorbent size, pH of the solution, initial concentration of the aqueous solution, dosage of biosorbent and temperature. The Central Composite Design (CCD) was used for final runs optimization using Response Surface Methodology (RSM). Results indicated that the optimum agitation time for biosorption of lead is 50 min. The increase in mass of biosorbent lead to increase in lead (pb) ion biosorption due to the increase in the number of active biosorption sites. Maximum percentage biosorption is observed at a pH of 6 and with particle size of 53 µm. Experimental data were better described by pseudo- second-order model. The adsorption isotherm could be well fitted by the Langmuir equation followed by Freundlich and Temkin. Over and all, Albizia Saman leaf powder can be used as an effective natural biosorbent for the economic treatment of aqueous solutions containing lead. Keywords - Albizia Saman, biosorption, optimization, isotherms, kinetics 1. INTRODUCTION Because of its relative recent development in the planet's history, pollution is a human problem. Before the 19th century Industrial Revolution, people lived more in harmony with their immediate environment. If one or more substances have built up in resources like water, air etc., to such an extent that they cause problems for living beings, we treat it as polluted one. As industrialization has spread around the globe, the problem of pollution spread along with it. Intensive mining operations and processing of minerals to meet the increasing needs of our society have led to environmental pollution in specific locations all over the world [1]. Heavy metals are discharged from various industries such as electroplating, plastic manufacturing, textile, storage batteries, mining and metallurgical process [2]. Water pollution of toxic heavy metal ions discharged from the industries and inhabited areas is seriously harmful to the health of human beings and the eco-system. Among these heavy metals, lead may be the severe pollutant sources due to its wide applications in industries, which may produce wastewater containing lead at the concentrations higher than the recommended doses of 0.015 mg/L. Microorganisms immobilized on natural and synthetic adsorbents have been used for separation and preconcentration of heavy metals at trace levels [3, 4, 5, 6, 7]. Most studies have focused on the removal of Pb2+, Cd2+, and Ni2+ from wastewater by using various biosorbents [8]. Biosorbents are prepared from the naturally abundant or waste biomass of algae, moss, fungi or bacteria [9]. Hence the naturally and abundantly available albizia saman has been selected for the present study for the removal of lead from aqueous solutions. 2. MATERIALS AND METHODS 2.1 Biosorbent Preparation Albizia saman leaves were obtained from Rajahmundry. The leaves are washed thrice with tap water and once with distilled water in order to remove adhering mud, impurities etc. It was dried in sunlight for one week until all the moisture was evaporated. The crispy powder were then crushed and grinded to powder, separated using British Standard Sieves (BSS) and stored in dry vacuum packs to prevent moisture content and readily used as biosorbent. 2.2 Batch sorption studies Preliminary experiments were conducted in 250 ml Erlenmayer flasks containing 50 ml of 20 mg/L metal solution using single step optimization procedure. The flasks were agitated on an orbital shaker at 180 rpm and samples were taken at predetermined time intervals (1, 3, 5, 10, 15, 20, 25, 30, 40, 50, 60, 90, 120, 150 & 180 min) & centrifuged at 14000 rpm and the supernatant liquid was analysed in Atomic Absorption Spectrophotometer (AAS) for final concentrations. Similarly the other variables were varied in a wide range: Biosorbent Size (53, 75, 104, 125 & 152 µm), pH of the aqueous solution (2, 3, 4, 5, 6, 7 and 8), Initial concentration of lead solution (25, 30, 60, 120 & 180 mg/L), Biosorbent Dosage (10, 20, 30, 40, 50 & 60 g/L) and Temperature (283, 293, 303, 313 & 323 K). 2.3 Process optimization ISSN: 2250-3013 www.iosrphr.org 579 | P a g e
  • 2. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 Final experimental runs for optimization were obtained through Response Surface Methodology from Design of Experiments (DoE) using STATISTICA software. The extent of biosorption of lead calculated at the preliminary optimum conditions is verified with the final runs for the optimum conditions. 3. RESULTS AND DISCUSSION The potential of dry Albizia saman leaf powder as a biosorbent for the biosorption of lead metal present in an aqueous solution is investigated in the present investigation. The effects of various parameters on biosorption of lead are studied. The numerical analysis of the investigation was undertaken applying CCD using RSM. 3.1 Effect of agitation time The equilibrium agitation time is determined by plotting the % biosorption of lead against agitation time as shown in fig. 1. For 0.5g (10 mg/L) of biosorbent and 53μm of biosorbent size in the interaction time intervals of 1 to180 min 58.30 % (1.166 mg/g) of lead is biosorbed in the first 1 min. The % biosorptionis increased briskly up to 50 min reaching 79.45 % (1.589 mg/g). Beyond 50 min, the % biosorption is constant indicating the attainment of equilibrium conditions. The maximum biosorption of 79.45% (1.589 mg/g ) is attained for 50 min of agitation time with 10 g/L of 53 μm size biosorbent mixed in 50 mL of aqueous solution (C0=20 mg/L) [10, 11]. 3.2 Effect of biosorbent size The percentage biosorption is increased from 72.12 (1.4424 mg/g) to 79.45 % (1.589 mg/g) as the biosorbent size decreases from 152 to 53 μm presented in fig. 2. This phenomenon is expected, as the size of the particle decreases, surface area of the biosorbent increases; thereby the numbers of active sites on the biosorbent are better exposed to the biosorbate. 3.3 Effect of pH of the aqueous solution In order to determine the optimal value, pH of the aqueous solution is varied from 2 to 8. The pH of aqueous solution is shown against % biosorption of lead in fig 3. The % biosorption of metal is increased from 58.42 % (1.1684 mg/g) to 77.18 % (1.5436 mg/g) as pH is increased from 2 to 6 and decreased beyond pH value of 7. The predominant sorbing forms of lead are Pb2+ and PbOH+ that occurr in the pH range of 4–6. This is the reason for higher biosorption of lead in the pH range of 4–6. At pH higher than 6, precipitation of lead occurred and biosorption due to biosorption is reduced [12, 13, 14]. 3.4 Effect of initial concentration of lead in the aqueous solution The effect of initial Pb2+ ion concentration is investigated in the range of 20-180 mg/L. The effect of initial concentration of lead in the aqueous solution on the percentage biosorption of lead is shown in fig. 4. The percentage biosorption of lead is decreased from 77.12% to 58.68% with an increase in C0 from 20 mg/L to 180 mg/L while the uptake capacity is increased from 1.5424 to 10.5624 mg/g [15]. 3.5 Effect of biosorbent dosage The biosorption of lead increases from 77.14% (1.5428 mg/g) to 83.78 % (0.5585 mg/g) with an increase in biosorbent dosage from 10 to 30 g/L, shown in fig. 5. Such behavior is obvious because with an increase in biosorbent dosage, the number of active sites available for lead biosorption would be more. The change in percentage biosorption of lead is marginal from 83.78% (0.5585 mg/g) to 84.92% (0.2830 mg/g) when ‘w’ is increased from 30 to 60 g/L. Hence all other experiments are conducted at 30 g/L dosage. 3.6 Effect of temperature The effect of temperature on the equilibrium metal uptake was significant. The effect of changes in the temperature on the lead uptake is shown in fig. 6. When temperature was lower than 303 K, Lead uptake increased with increasing temperature, but when temperature was over 303 K, the results slowed down and the increase is marginal. This response suggested a different interaction between the ligands on the cell wall and the metal. Below 303 K, chemical biosorption mechanisms played a dominant role in the whole biosorption process, biosorption was expected to increase by increase in the temperature. While at higher temperature, the plant powder was in a nonliving state, and physical biosorption became the main process. Physical biosorption reactions were normally exothermic, thus the extent of biosorption generally is constant with further increasing temperature [16]. ISSN: 2250-3013 www.iosrphr.org 580 | P a g e
  • 3. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 3.7 Isotherms 3.7.1 Langmuir isotherm Irving Langmuir developed an isotherm named as Langmuir isotherm, which is the most widely used simple two- parameter equation. Langmuir isotherm is drawn between Ce vs Ce/ qe shown in fig 7. The equation obtained is (Ce/qe) = 2.8729 Ce + 0.05929 with a good linearity (correlation coefficient, R2=0.9791) indicating strong binding of lead ions to the surface of albizia saman leaf powder. The separation factor (RL) of 0.9219 shows favorable biosorption (0< RL<1). Hence a maximum biosorption capacity of the Albizia saman leaf powder for lead is find to be 16.8656 mg/g by Langmuir isotherms at 303K (mass of biosorbent: 10 g/L) [17, 18]. 3.7.2 Freundlich isotherm Freundlich empirical adsorption isotherm equation can be applied in case of low and intermediate concentration ranges. Freundlich isotherm is drawn between log qe and log Ce, in fig. 8 The equation obtained is log qe = 0.6815 log Ce – 0.2404. The resulting equation has a correlation coefficient of 0.9655. The ‘n’ value in the above equations is 0.6815, satisfies the condition of 0<n<1 indicating favorable biosorption. Kf is 0.5748 mg/g [19]. 3.7.3 Temkin isotherm Temkin and Pyzhev isotherm equation describes the behavior of many adsorption systems on the heterogeneous surface. The present data are analysed according to the linear form of Temkin isotherm and the linear plot is shown in fig. 9 The equation obtained for lead biosorption is: q e = 3.1546 ln Ce -3.8813 with a correlation coefficient 0.9637. The best fit model is determined based on the linear regression correlation coefficient (R2) [20]. 3.8 Kinetics of biosorption Kinetic models are used to describe the order of biosorbate – biosorbent interactions. Traditionally, the first order model of Lagergren finds wide application. In the case of biosorption preceded by diffusion through a boundary, the kinetics in most cases follows the first order rate equation of Lagergren [21]: (dqt/dt) = K1 (qe – qt) where qe and qt are the amounts adsorbed at t, min and equilibrium time and Kad is the rate constant of the first order adsorption. The above equation can be presented as log (qe – qt) = log qe – (K1/2.303) t log (qe – qt) = –0.02357 t – 0.3027 ; R2 = 0.9620 Plot of log (qe–qt) versus ‘t’ gives a straight line for first order kinetics, facilitating the computation of biosorption rate constant (K1). If the experimental results do not follow the above equation, they differ in two important aspects: K1 (qe – qt) does not represent the number of available adsorption sites and log q e is not equal to the intercept. In such cases, pseudo second order kinetic equation [22, 23]: (dqt/dt ) = K2 (qe – qt)2 is applicable, where ‘K2’ is the second order rate constant. The other form of the above equation is: (t/qt) = (1/ K2qe2) + (1/qe) t (t/qt) = 0.6229 t + 1.1720; R2 = 0.9959 The pseudo second order model based on above equation, considers the rate-limiting step as the formation of chemisorptive bond involving sharing or exchange of electrons between the biosorbate and biosorbent. If the pseudo second order kinetics is applicable, the plot of (t/qt) versus ‘t’ gives a linear relationship that allows computation of q e and K2. In the present study, the kinetics are investigated with 50 mL of aqueous solution (C 0= 20 mg/L) at 303 K with the interaction time intervals of 1 min to 50 min. Lagergren and pseudo plots for biosorption of lead with biosorbent size 53 μm of Albizia saman leaf powder are drawn in figs. 10 & 11. As the correlation coefficient values for the pseudo second order kinetics is 0.99 which is better than first order kinetics (R2=0.962), very well describes the biosorption mechanism of lead using Albizia saman leaf powder. 3.9 Thermodynamics of biosorption The process of Biosorption is temperature dependant. In general, the temperature dependence is associated with three thermodynamic parameters namely change in enthalpy of biosorption (∆H), change in entropy of biosorption (∆S) and change in Gibbs free energy (∆G). The Van’t Hoff’s plots for the biosorption data obtained at initial concentrations of the lead are shown in fig. 12. The equation obtained is log qe / Ce = –0.41701(1/T) + 0.5921. The correlation coefficient is 0.9568. In the present study, the enthalpy change is ∆H is 7.9845 J/mole is positive indicating that the biosorption is endothermic. The value of ∆S is 11.3370 J/mole is also positive indicating the irreversibility of process, ∆G is 3427.1334 J/mole is negative indicating the spontaneity of biosorption. ISSN: 2250-3013 www.iosrphr.org 581 | P a g e
  • 4. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 3.10 Optimization of the selected parameters using CCD In order to determine an optimum condition for lead ions removal, the parameters having greater influence over the response are to be identified. In the present study, the relationship between four independent variables and percent of lead ions biosorption is fitted well with the quadratic model. The regression equation for the optimization of lead biosorption: % biosorption of lead (Y) is a function of the W (X1), Co (X2), pH (X3), and T (X4). Table–1 presents the coded levels and Table– 2 represents the variations in the corresponding coded values of four parameters and response based on experimental runs and predicted values proposed by CCD design. Y = –452.007 + 0.429 X1 + 0.369 X2 + 5.846 X3 + 3.347 X4 – 0.006X12 – 0.015X22 – 0.548 X32 – 0.006 X42 + 0.004 X1X2 – 0.010 X1X3 + 0.026 X2X3 + 0.002 X3X4 -------------------------------- (1) Interpretation of the regression analysis: The results of above regression model for Eq. (1) (in the form of analysis of variance ANOVA) are compiled in Table-3. In general, the Fischer’s ‘F-statistics’ value (=MSmodel/MSerror), where MS (mean square) with a low probability ‘P’ value indicates high significance of the regression model. The ANOVA of the regression model demonstrates that the model is highly significant, as is evident from the Fisher’s F-test (Fmodel = 33852) and a very low probability value (Pmodel > F=0.000000). More over, the computed F-value (F0.05 (14.15) = MSmodel/MSerror = 33852) is greater than that of the tabular F- value (F0.05 (14.15) tabulars = 2.42) at the 5% level, indicating that the treatment differences are significant. The significance of the regression coefficient of the parameter can be verified by the Student’s t-test as a tool, while ‘P’ values signify the pattern of interaction among the factors. From the Table–4, we can observe that, the larger the value of t and smaller the value of P, more significant is the corresponding coefficient term. By analyzing the ‘t’ values and ‘P’ values from Table-4, it is found that the X1, X2, X3, X4, X12 , X22 , X32 , X42 X1X2, X1X3, X1X4, X2X3, X2X4, X3X4 have high significance to explain the individual and interaction effect of biosorption variables on the biosorption of lead to predict the response. A positive sign of the coefficient represents a synergistic effect which means response (% biosorption of lead increases with the increase in effect, while a negative sign indicates an antagonistic effect which means response (% biosorption of lead) decreases with the increase in effect. The optimal set of conditions for maximum percentage biosorption of lead is pH = 6.0250, biosorption dosage (w) = 31.7191 g/L, initial lead concentration (C o) = 19.8996 mg/L and temperature = 304.0673 K. The extent of biosorption of lead calculated at these optimum conditions is 84.90612%. Fig. 13 shows the comparison between the % biosorption obtained through experiments and predicted. The correlation coefficient (R2) provides a measure of the models variability in the observed response values. The closer the R2 value to 1, the stronger the model is and it predicts the response better. In the present study the value of the regression coefficient (R 2 = 0.99997) indicates that 0.003% of the total variations are not satisfactorily explained by the model. The ANOVA Table-3 can be used to test the statistical significance of the ratio of mean square due to regression and mean square due to residual error. Figs. 15 to 20 were represented as a function of two factors at a time, holding other factors fixed at zero level for the Interaction effects of biosorption variables. ISSN: 2250-3013 www.iosrphr.org 582 | P a g e
  • 5. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 4. FIGURES AND TABLES 85 biosorbent=albizia saman leaf power 80 %biosorption of lead 75 Dp=53m w=10g/L T=303K 70 C0=20mg/L pH=6.8 65 % biosorption of lead 60 55 0 20 40 60 80 100 120 140 160 180 200 agitation time, t min Fig. 1 Effect of agitation time on % biosorption of lead 90 1.60 88 Biosorbent = Albizia saman leaf power 1.58 86 1.56 W=10g/L T= 303K % biosorption of lead 84 pH= 6.8 1.54 t =50min metal uptake 82 C0=20mg/L 1.52 80 1.50 78 1.48 76 1.46 74 % biosorption 72 metal uptake 1.44 70 1.42 40 60 80 100 120 140 160 Biosorbent size m Fig. 2 Variations in % biosorption of lead using biosorbent sizes 80 2.0 Biosorbent= Albizia saman leaf power 75 1.8 % biosorption % biosorption of lead metal uptake metal uptake 70 1.6 65 1.4 Dp=53m T=303K W=10 g/L t = 50min 60 1.2 C0=20 mg/L 55 1.0 1 2 3 4 5 6 7 8 9 pH of aqueous solution Fig. 3 Effect of pH on % biosorption of lead ISSN: 2250-3013 www.iosrphr.org 583 | P a g e
  • 6. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 80 12 Biosorbent= Albizia saman leaf power 10 75 % biosorption metal uptake % biosorption of lead 8 metal uptake 70 6 65 4 Dp=53m T=303K 60 pH= 6 2 W=10g/L t =50min 55 0 0 20 40 60 80 100 120 140 160 180 200 initial concentration of aqueous solution, mg/L Fig. 4 Effect of initial concentration for the biosorption of lead 86 1.8 Biosorbent =Albizia saman leaf power 1.6 84 1.4 % biosorption % Biosorption of lead metal uptake 1.2 Metal uptake 82 Dp=53m 1.0 T=303K 80 pH=6 C0=20mg/L 0.8 t=50min 0.6 78 0.4 76 0.2 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Biosorbent dosage, W, g/L Fig. 5 Effect of biosorbent dosage on % biosorption of lead 86 Biosorbent = Albizia saman leaf powder 85 0.58 % biosorption 84 metal uptake % biosorption of lead 0.56 83 metal uptake 82 Dp=53m pH=6 0.54 C0=20 mg/L 81 W=30 g/L t=50min 80 0.52 79 78 0.50 280 290 300 310 320 330 Temperature, K Fig. 6 Effect of temperature for the biosorption of lead ISSN: 2250-3013 www.iosrphr.org 584 | P a g e
  • 7. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 8 Biosorbent = Albizia saman leaf power 7 91 .97 2 =0 6 ,r 92 92 .05 Ce/qe gm/L +0 C e 29 5 .87 =2 /q e Dp= 53 m C e W = 10 g/L 4 T =303 K pH =6.0 t = 50min 3 2 0 10 20 30 40 50 60 70 80 Ce Fig. 7 Langmuir isotherm for biosorption of lead 1.2 Biosorbent = Albizia saman leaf power 1.0 55 .96 0.8 2 =0 ,r 04 24 -0. Ce log qe log 0.6 15 .68 =0 Dp= 53 m q e log W = 10 g/L 0.4 T =303 K pH =6.0 t = 50min 0.2 0.0 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 log Ce Fig. 8 Freundlich isotherm for biosorption of lead -2 Biosorbent = Albizia saman leaf power 0 q e =3 .15 46 2 lnC e- -3 .88 13 ,r2 Dp= 53 m =0 .96 qe 4 37 W = 10 g/L T =303 K pH =6.0 t = 50min 6 8 10 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 ln Ce Fig. 9 Temkin isotherm for biosorption of lead ISSN: 2250-3013 www.iosrphr.org 585 | P a g e
  • 8. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 -1.4 Biosorbent = Albizia saman leaf power -1.2 20 .96 2 =0 ,r 27 -1.0 .30 7 t-0 35 02 -0. )= log (qe-qt) -0.8 -q t (q e log Dp= 53 m -0.6 W = 10 g/L T =303 K pH =6.0 -0.4 C0=20 mg/L -0.2 0.0 0 10 20 30 40 50 t, min Fig. 10 First order kinetics for biosorption of lead 35 Biosorbent = Albizia saman leaf power 30 25 59 2 0. 99 20 r= 0, 72 t+1.1 t/qt 15 9 Dp= 53 m 22 =0.6 W = 10 g/L t/q t T =303 K 10 pH =6.0 C0=20 mg/L 5 0 0 10 20 30 40 50 60 t, min Fig. 11 Second order Kinetics for biosorption of lead -0.65 Biosorbent = Albizia saman leaf power -0.70 log q/ e C e =-0 -0.75 .41 70 (1 / t) +0 logqe/Ce .59 21 -0.80 , r2 Dp= 53 m =0.9 56 W = 10 g/L 8 t =50 min -0.85 pH =6.0 C0=20 mg/L0=20 mg/L -0.90 -0.95 3.0 3.1 3.2 3.3 3.4 3.5 3.6 1/t x 103min Fig. 12 Vant Hoff’s plot for biosorption of lead ISSN: 2250-3013 www.iosrphr.org 586 | P a g e
  • 9. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 Fig. 13 Predicted vs Observed Fig. 14 Pareto Chart Fig. 15 Surface contour plot for the effects of dosage and initial concentration of lead on % biosorption ISSN: 2250-3013 www.iosrphr.org 587 | P a g e
  • 10. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 Fig. 16 Surface contour plot for the effects of dosage and pH on % biosorption of lead Fig. 17 Surface contour plot for the effects of dosage & Temperature on % biosorption of lead Fig. 18 Surface contour plot for the effects of initial concentration and pH on % biosorption of lead ISSN: 2250-3013 www.iosrphr.org 588 | P a g e
  • 11. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 Fig. 19 Surface contour plot for the effects of initial concentration and Temperature on % biosorption of lead Fig. 20 Surface contour plot for the effects of pH and Temperature on % biosorption of lead TABLE–1 Levels of different process variables in coded and un-coded form for % biosorption of lead using Albizia saman leaf powder Var Name Range and levels -2 -1 0 1 2 X1 Biosorbent dosage, 10 20 30 40 50 w, g/L X2 Initial concentration, 10 15 20 25 30 Co, mg/L X3 pH of aqueous 4 5 6 7 8 solution X4 Temperature, T, K 283 293 303 313 323 ISSN: 2250-3013 www.iosrphr.org 589 | P a g e
  • 12. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 TABLE–2 Results from CCD for lead biosorption by Albizia saman leaf powder Runs X1, W X2, Co X3, pH X4, T Experimental Predicted 1 -1.00 -1.00 -1.00 -1.00 82.70 82.70 2 -1.00 -1.00 -1.00 1.00 82.98 82.98 3 -1.00 -1.00 1.00 -1.00 82.72 82.71 4 -1.00 -1.00 1.00 1.00 83.06 83.05 5 -1.00 1.00 -1.00 -1.00 81.94 81.93 6 -1.00 1.00 -1.00 1.00 82.16 82.15 7 -1.00 1.00 1.00 -1.00 82.44 82.44 8 -1.00 1.00 1.00 1.00 82.76 82.75 9 1.00 -1.00 -1.00 -1.00 82.96 82.96 10 1.00 -1.00 -1.00 1.00 83.14 83.13 11 1.00 -1.00 1.00 -1.00 82.54 82.54 12 1.00 -1.00 1.00 1.00 82.80 82.80 13 1.00 1.00 -1.00 -1.00 83.04 83.04 14 1.00 1.00 -1.00 1.00 83.18 83.18 15 1.00 1.00 1.00 -1.00 83.16 83.15 16 1.00 1.00 1.00 1.00 83.36 83.36 17 -1.00 0.00 0.00 0.00 82.04 82.04 18 2.00 0.00 0.00 0.00 82.92 82.91 19 0.00 -2.00 0.00 0.00 83.50 83.49 20 0.00 2.00 0.00 0.00 83.28 83.28 21 0.00 0.00 -2.00 0.00 82.60 82.59 22 0.00 0.00 2.00 0.00 82.78 82.78 23 0.00 0.00 0.00 -2.00 82.44 82.43 24 0.00 0.00 0.00 2.00 82.92 82.92 25 0.00 0.00 0.00 0.00 84.88 84.88 26 0.00 0.00 0.00 0.00 84.88 84.88 27 0.00 0.00 0.00 0.00 84.88 84.88 28 0.00 0.00 0.00 0.00 84.88 84.88 29 0.00 0.00 0.00 0.00 84.88 84.88 30 0.00 0.00 0.00 0.00 84.88 84.88 Table–3 ANOVA of lead biosorption for entire quadratic model Mean Source of variation SS df F-value P>F square(MS) Model 24.3289 14 1.737778 33852.82 0.0000 Error 0.00077 15 0.0000513 Total 24.32967 Df- degree of freedom; SS- sum of squares; F- factor F; P- probability. R2=0.99997; R2 (adj):0.99994 ISSN: 2250-3013 www.iosrphr.org 590 | P a g e
  • 13. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 Table–4 Estimated regression coefficients for the lead biosorption onto Albizia saman leaf powder Terms Regression Standard error of t-value P-value coefficient the coefficient Mean/Intercept -452.007 1.335753 -338.391 0.000000 Dosage, w, g/L (L) 0.429 0.005629 76.293 0.000000 Dosage, w, g/L (Q) -0.006 0.000014 -439.689 0.000000 Conc, Co, mg/L (L) 0.369 0.011310 32.663 0.000000 Conc, Co, mg/L (Q) -0.015 0.000055 -273.032 0.000000 pH (L) 5.846 0.057298 102.035 0.000000 pH (Q) -0.548 0.001365 -401.230 0.000000 Temperature, T, K (L) 3.347 0.008391 398.867 0.000000 Temperature, T, K (Q) -0.006 0.000014 -403.061 0.000000 1L by 2L 0.004 0.000036 120.992 0.000000 1L by 3L -0.010 0.000179 -58.048 0.000000 1L by 4L -0.000 0.000018 -13.288 0.000000 2L by 3L 0.026 0.000357 72.036 0.000000 2L by 4L -0.000 0.000036 -6.294 0.000014 3L by 4L 0.002 0.000179 10.491 0.000000 5. CONCLUSION Both Preliminary and finals experimental runs are carried out to find out the equilibrium, isotherms, kinetics and thermodynamic parameters for biosorption of lead from an aqueous solution using Albizia saman leaf powder. The analysis of the experimental and theoretical data results in the conclusions that the equilibrium agitation time for lead biosorption is 50 minutes. The % biosorption of lead from an aqueous solution increased from 72.12 to 79.45 % with a decrease in the particle size of the biosorbent from 152 to 53 µm and increases from 77.14 to 83.78 % with increase in biosorbent dosage from 10 to 30 g/L. With an increase in the initial concentration of lead in the aqueous solution (20 to 180 mg/L), the percentage biosorption of lead from the aqueous solution is decreased from 77.12 to 58.68 %. Percentage biosorption of lead from the aqueous solution increased significantly with increase in pH from 2 to 6 (58.42 to 77.18 %). Hereafter, percentage biosorption decreases for further increase in pH from 6 to 8 (77.18 to 69.42 %). The maximum uptake capacity of 16.8656 mg/g is obtained at a temperature of 303 K. The present study involves the use of statistical experimental design to optimize process conditions for maximal biosorption of lead from aqueous solution using CCD involving RSM. The maximum biosorption of lead (84.90612 %) onto Albizia saman leaf powder is observed when the processing parameters are set as follows: pH = 6.0250, w = 31.7191 g/L, Co = 19.8996 mg/L and T = 304.0673 K. The kinetic studies showed that the biosorption of lead is better described by pseudo second order kinetics. The thermodynamic data depicted that % biosorption of lead increased with increase in temperature up to some extent. ISSN: 2250-3013 www.iosrphr.org 591 | P a g e
  • 14. IOSR Journal of Pharmacy Vol. 2, Issue 3, May-June, 2012, PP.579-592 REFERENCES [1] Prerna Ahuja, Rani Gupta, R.K. Saxena, Sorption and Desorption of Cobalt by Oscillatoria anguistissima, Current Microbiology Vol. 39, 1999, pp. 49–52 [2] Ahmet Çabuk, Tamer Akar, Sibel Tunali, Özge Tabak, Biosorption characteristics of Bacillus sp. ATS-2 immobilized in silica gel for removal of Pb(II), Journal of Hazardous Materials, Volume 136, Issue 2, 21, 2005, Pages 317–323 [3] Volesky, B., Removal and recovery of heavy metals by biosorption [C] Volesky B, ed. Biosorption of Heavy Metals (Boca Raton: CRC Press, 1990) 12–13. [4] Volesky, B, Biosorption of Heavy Metals (CRC Press, Boca Raton 1990). [5] Lo, W., Chua, H., Lam, K.H., Bi, S.P., A comparative in`vestigation on the biosorption of lead by filamentous fungal biomass, Chemosphere 39, 1999, 2723–2736. [6] Alaa H. Hawari, Catherine N. Mulligan, Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass, Bioresource Technology 97, 2006, 692–700. [7] Ankit Balaria, Silke Schiewer, Assessment of biosorption mechanism for Pb binding by citrus pectin, Separation and Purification Technology 63, 2008, 577–581. [8] Anushree Malik, Metal bioremediation through growing cells, Environment International 30, 2004, 261– 278. [9] Arzu,Y.and Dursun,A., Comparative study on determination of the equilibrium, kinetic and thermodynamic parameters of biosorption of copper (II) and lead (II) ions onto pretreated Aspergillus niger, Biochem.Eng. J., 28, 2006, 187-195. [10] Chandrasekhar K, Subramanian S, Modak JM, Natarajan KA, Removal of metals using an industrial biomass with reference to environmental control, Int J Miner Process 53, 1998, 107–120. [11] K. Parvathi, R. Nareshkumar R. Nagendran, Biosorption of lead by Aspergillus niger and Saccharomyces cerevisiae, World J Microbiol Biotechnol 23, 2007, 671–676. [12] R.N. Sylva, The environmental chemistry of copper (II) in aquatic systems, Water Res. 10, 1976, 789–792. [13] O. Masala, E.J.L. McInnes, P. Obrien, Modelling the formation of granules: the influence of lead ions on calcium pyrophosphate precipitates, Inorg, Chim. Acta 339, 2002, 366–372. [14] Goyal N, Jain SC, Banerjee, Comparative studies on the microbial adsorption of heavy metals, Adv Environ Res 7, 2003, 311–319. [15] Sag, Y., D. Ozer and T. Kutsal, A comparative study of the biosorption of lead(II) ions to Z. ramigera and R. arrhizus, Process Biochem., 30, (2), 1995, 169-174. [16] R.H.S.F. Vieira, B. Volesky, Biosorption: a solution to pollution, Int. Microbiol. 3, 2000, 17–24. [17] I. Langmuir, The constitution and fundamental properties of solids and liquids. Part 1: Solids, J. Am. Chem. Soc., 38, 1916, 2221–2295. [18] I. Langmuir, The adsorption of gases on plane surface of glass, mica and platinum, J. Am. Chem. Soc., 40, 1918, 1361–1403. [19] H. Freundlich, Uber die adsorption in losungen (Adsorption in solution), Z. Phys. Chemie., 57, 1906, 384- 470. [20] M.J Temkin and V Pyzhey, Recent modifications to Langmuir isotherms, Acta Physiochim., 12, 1940, 217– 222. [21] S. Lagergren, On the theory of so called adsorption of dissolved substances, Handlingar, 24, 1898, 1–39. [22] Y.S. Ho and G McKay, A Comparison of Chemisorption Kinetic Models Applied to Pollutant Removal on Various Sorbents, Process Safety and Environmental Protection, 6B, 1998, 332-340. [23] Y.S. Ho and G. McKay, Pseudo-second order model for sorption processes, Process Biochemistry, 34, 1999, 451–465. ISSN: 2250-3013 www.iosrphr.org 592 | P a g e