Ind. Eng. Chem. Res.

2007, 46, 5697-5706 5697

Multicomponent Adsorption Study of Metal Ions onto Bagasse Fly Ash Using
Taguchis Design of Experimental Methodology
Vimal C. Srivastava,* Indra D. Mall, and Indra M. Mishra
Department of Chemical Engineering, Indian Institute of Technology-Roorkee, Roorkee 247667, India

This paper utilizes the Taguchi optimization methodology (L27 orthogonal array) to optimize various parameters
for the simultaneous removal of Cd, Ni, and Zn metal ions from aqueous solutions using bagasse fly ash
(BFA) as an adsorbent. The effect of such parameters as the initial metal concentrations (C0,i), temperature,
initial pH, adsorbent dosage (m), and contact time on the adsorption of the aforementioned metal ions has
been studied at three levels to determine their effect on the selected response characteristic (the total amount
of metal adsorbed on BFA, in terms of mg/g of BFA (qtot)). The Pareto analysis of variance shows that m is
the most significant parameter, with a 53.14% and 31.25% contribution to the qtot and signal-to-noise (S/N)
ratio data. The contribution of interactions between the C0,i values is also significant. Confirmation experiments
have been performed to prove the effectiveness of the Taguchi technique after the optimum levels of process
parameters are determined.

1. Introduction
Heavy metals are toxic and resistant to biodegradation.
Because of their mobility in natural water ecosystems and
adsorption onto soils, sediments, thick sludge, etc., they ac-
cumulate in aquatic life forms such as fish, vegetation, and
horticultural products via the food chain. When consumed, these
metals accumulate in tissues, fats, and other organs of humans,
causing malfunctions and damage to vital functions of the bodys
system. In the past four decades, the uncontrolled discharge of
heavy metals from plating/rinsing industries and various other
manufacturing process industries has resulted in serious con-
tamination of numerous sites. The heavy-metal ions are often
encountered at elevated levels, and their exposure is likely to
persist for a prolonged time. The Central Pollution Control
Board, Ministry of Environment and Forests, Government of
India (CPCB), has set minimal national standards of 1.0, 3.0,
and 5.0 mg/L, respectively, for Cd(II), Ni(II), and Zn(II) for
the safe discharge of the industrial effluents that contain these
metal ions into surface waters.1
Several methods (e.g., physicochemical, biological, and
thermal processes) have been developed for the removal of
heavy metals from waters and wastewaters to decrease their
impact on the environment. Physicochemical processes apply
to all waste types, whereas biological methods are appropriate
for dilute wastewaters that contain metals and thermal techniques
are applicable to organometallics.2 The physicochemical treat-
ment processes mainly include adsorption, precipitation, and
ion exchange. Adsorption technologies for metals wastes include
activated carbon and ion exchange treatment. For high-strength
and low-volume wastewaters, the removal of heavy metals via
adsorption, using granular/powdered activated carbon, has been
widely used. Most of the activated carbons available com-
mercially are microporous and of high surface area, and exhibit
high efficiency for the adsorption of gaseous molecules.
However, the adsorption efficiency of bigger and high-molec-
ular-weight molecules on microporous activated carbon is very
low. Also, adsorbent-grade activated carbon is cost-prohibitive
* To whom correspondence should be addressed. Tel.: +91-1332-
285889. Fax: +91-1332-276535, 273560. E-mail address: vimalcsr@
yahoo.co.in.
10.1021/ie0609822 CCC: $37.00 2007 American Chemical Society
Published on Web 07/14/2007
and both regeneration and disposal of the used carbon is often
very difficult. Therefore, the search for unconventional and less-
expensive adsorbents such as bagasse fly ash (BFA), rice husk
ash, silica, peat, lignite, bagasse pith, wood, saw dust, etc. for
the removal of various pollutants from industrial effluents has
attracted the attention of several investigators.
BFA, which is a waste that is collected from the particulate
collection equipment attached upstream to the stacks of bagasse-
fired boilers, causes disposal problems. It is mainly used for
land filling, and it is used in part as a filler in building materials
and paper and wood boards. BFA has good adsorptive properties
and has been used for the removal of chemical oxygen demand
(COD) and color from paper mill effluents.3 Various researchers
have utilized it for the adsorptive removal of phenolic com-
pounds,4 pyridine,5 dyes,6-8 and metals.9-12 This waste material
is a potent low-cost adsorbent for the removal of heavy-metal
ions from industrial aqueous effluents.
Much of the work on the adsorption of heavy-metal ions by
various types of adsorbents has focused on the uptake of single
metals. Because of the fact that industrial effluents generally
contain several metals, it is necessary to study the simultaneous
sorption of two or more metals and also to quantify the
interference of one metal with the sorption of the other. No
information is available in the literature for the simultaneous
removal of Cd(II), Ni(II), and Zn(II) ions by BFA. However, it
has also been reported that the adsorption of metal ions from
aqueous solution by any adsorbent is drastically affected by
several factors, such as the initial concentration of metal ion
(C0), temperature (T), initial pH (pH0), adsorbent dosage (m),
and contact time (t). Generally, one-factor-at-a-time experi-
ments have been conducted in most of the previous studies to
determine the operating conditions of optimum metal removal.
One-factor-at-a-time designs often overlook interactive effects
of the factors on the sorption process. Fractional factorial design
based on Taguchis orthogonal array (OA) can be a very
effective methodology to investigate the effects of multiple
factors, as well as potential interactions between these factors,
in a time- and cost-effective manner.13 To date, no work is
available in the literature on the optimization of process
parameters based on Taguchis OA experimental design for the
simultaneous removal of metal ions. The objective of this paper
is to apply Taguchis fractional factorial experimental design
5698 Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007
to screen significant factors, which would have a great impact
on the multicomponent adsorption efficiency of metal ions from
aqueous solution using BFA as an adsorbent.
The objective of the present study is to maximize the selected
response characteristic (the total amount of metal ions adsorbed
onto BFA in terms of milligrams per gram of BFA (qtot)) by
optimizing the various parameters that affect the simultaneous
removal of Cd(II), Ni(II), and Zn(II) metal ions from aqueous
solutions by BFA. The effect of individual process parameters
and their interactions on qtot will be examined using the standard
procedure suggested by Taguchi. The mean or the average
values and S/N ratio of the quality/response characteristics for
each parameter at different levels have been calculated from
experimental data. For the graphical representation of the change
in value of quality characteristic, and that of S/N ratio with the
variation in process parameters, the response curves will be
plotted. These response curves are used to examine the
parametric effects on the response characteristics. The analysis
of variance (ANOVA) will be performed for the raw and
S/N data to identify the significant parameters and to
quantify their effect on the response characteristics. The most-
favorable conditions (optimal settings) of process parameters,
in terms of the mean response of characteristics, would be
established by analyzing the response curves and the ANOVA
tables.
2. Materials and Methods
2.1. Adsorbent and Adsorbates. BFA was obtained from a
nearby sugar mill (Deoband Sugar Mill, U.P., India) and used
as an adsorbent without any pretreatment (except sieving).
Detailed physicochemical characteristics of the BFA have
already been presented elsewhere.4,9
All the chemicals used in the study were analytical reagent
grade. Nickel chloride hexahydrate (NiCl26H2O) was procured
from Qualigens Fine Chemicals, Mumbai, India. Cadmium
sulfate octahydrate (3CdSO48H2O), zinc sulfate heptahydrate
(ZnSO47H2O), NaOH, HCl, HNO3, H2SO4, and CH3COOH
were obtained from s.d. fine chemicals, Mumbai. Stock solutions
of Cd(II), Ni(II), and Zn(II) metal ions (1 g/L strength) were
prepared by dissolving exact amounts of 3CdSO48H2O, NiCl2
6H2O, and ZnSO47H2O separately in double-distilled water. The
stock solution for each metal salt was diluted to give metal-ion
concentrations in the range of 0-100 mg/L for use in the
experiments.
2.2. Analysis of Metal Ions. The concentration of Cd(II),
Ni(II), and Zn(II) in the aqueous samples was determined using
a flame atomic absorption spectrophotometer (GBC Avanta,
Australia) with the detection limit of 0.009, 0.040, and 0.008
mg/L at wavelengths of 228.8, 232, and 213.9 nm, for Cd(II),
Ni(II), and Zn(II), respectively, using an air-acetylene flame.
Before the analysis, the sample was diluted, if necessary, with
distilled water to a concentration in the range of 0.2-1.8 mg/L
for Cd(II), 1.8-8 mg/L for Ni(II) and 0.4-1.5 mg/L for Zn-
(II). Metal-ion concentrations were determined with reference
to the appropriate standard metal-ion solutions.
2.3. Taguchis Methodology of Experimental Design.
Taguchis methodology has been used extensively in conducting
experiments and devising a strategy for the quality control of
products in the manufacturing industries. Taguchis method to
improve the quality of the products is heavily dependent on
designing and testing a system based on engineers judgment
of selected materials and parts, and nominal product/process
parameters based on current technology.14 Although system
Table 1. Process Parameters for Multicomponent Adsorption Study
of Metal Ions onto BFA Using Taguchis Orthogonal Arrays (OAs)
parameter level 0 level 1 level 2
A initial concentration of cadmium, 0 50 100
C0,Cd (mg/L)
B initial concentration of nickel, 0 50 100
C0,Ni (mg/L)
C initial concentration of zinc, 0 50 100
C0,Zn (mg/L)
D temperature, T (C) 20 30 40
E initial pH of solution, pH0 4 6 8
F BFA dose, m (g/L) 5 10 15
G contact time, t (min) 30 60 90
design helps to identify the working levels of the design
parameters, process parameter design seeks to determine the
parameter levels that produce the best performance of the
product/process under study. The optimum condition is selected
so that the influence of uncontrollable factors (noise factors)
causes minimum variation to the system performance. The OAs,
variance, and S/N analysis are the essential tools of parameter
design.
Taguchis method of experimental design provides the optimal
selection of parametric values, based on their intraparametric
interaction, to accomplish a process. This method minimizes
the number of experiments to be conducted based on the
statistical significance of parameters and the interactive influ-
ences of these parameters.
Taguchis methodology, as adopted in this study, consists of
four phases (with various steps), viz., planning, conducting,
analysis, and validation. Taguchis method of design of experi-
ments (DOE) involves the establishment of a large number of
experimental situations, described as OAs, to reduce experi-
mental errors and to enhance their efficiency and the reproduc-
ibility of the laboratory experiments. Each phase has separate
objectives that are interconnected sequentially to achieve the
overall optimization process.
2.3.1. Design of Experiment (Phase 1). The first step in
Phase 1 is to identify the various factors to be optimized in
batch experiments that have critical effect on the simultaneous
adsorptive removal of Cd(II), Ni(II), and Zn(II) metal ions from
aqueous solutions adsorption onto BFA. Factors were selected
and the ranges were further assigned based on the detailed
experiments for metal removal using BFA.9-12 Based on the
experience, seven process parameters that exerted significant
influence on the metal adsorption have been selected for the
present experimental design. These process parameters, as well
as their designations and levels, are given in Table 1. The initial
concentration of one metal ion (C0,i) significantly affects the
adsorption of other metal ions in the simultaneous adsorption
of metal ions;9,10 therefore, it has been decided to study three
two-parameter interactions between the initial concentrations
of metal ions, i.e., C0,Cd C0,Ni, C0,Cd C0,Zn, and C0,Ni
C0,Zn.
2.3.1.1. Selection of Orthogonal Array (OA) and Param-
eter Assignment. The next step in phase 1 was to design the
matrix experiment and define the data analysis procedure. The
appropriate OAs for the control parameters to fit a specific study
were selected. Taguchi provides many standard OAs and
corresponding linear graphs for this purpose. The OA selected
must satisfy the following inequality:
total DOF of the OA g
total DOF required for the experiment

where DOF denotes the degrees of freedom. It was decided to
study each selected process parameter at three levels to account
for nonlinear behavior (if any) of the parameters of a process.15
With seven parameters each at three levels and three second-
order interactions, the total DOF required is 26 [ ) 7 (3 -
1) + (3 4)], because a three-level parameter has DOF ) 2
(number of levels ) 1) and each two-parameter interaction term
has DOF ) 4 (2 2). Hence, an L27 (313) OA (a standard three-
level OA) has been selected for this phase of work. The L27
OA, with the assignment of parameters and interactions, is
shown in Table 2. The parameters and interactions have been
assigned to specific columns of the OA using the triangular
table.16
2.3.2. Batch Experimental Adsorption Studies (Phase 2).
Batch adsorption experiments were performed for simultaneous
metal removal with BFA, using the selected 27 experimental
trials, in combination with seven process factors at three
levels (Table 1), and the result obtained from each set, in
terms of the total amount of metal ion adsorbed onto BFA
(in mg/g of BFA) (qtot) is shown in Table 2. The results
presented in the table represent those for three individual
determinations.
For each experimental run, 150 mL of aqueous solution,
having 50 mL of each metal ion solution (viz. Cd(II), Ni(II),
and Zn(II)) of known concentration was taken in a 500-mL
stoppered conical flask that contained a specific amount of BFA.
These flasks were agitated at a constant shaking rate of 150
rpm in a temperature-controlled orbital shaker (Remi Instru-
ments, Mumbai, India) maintained at 20, 30, or 40 C. The
initial pH (pH0) of the adsorbate solution was adjusted using 1
N (36.5 g/L) HCl or 1 N (40 g/L) NaOH aqueous solution
without any further pH adjustment during the sorption process.
The samples withdrawn after appropriate contact time were
centrifuged using Research Centrifuge (Remi Instruments,
Mumbai, India) at 5000 rpm for 5 min, and then the supernatant
liquid was analyzed for the residual concentration of metal
ions.
The removal of metal ions from the solution and the
equilibrium adsorption uptake in the solid phase, qtot (in units
of mg/g), were calculated using the following relationship:
3 C0,i - Ce,i
qtot )
i)1 m
(1)
where C0,i is the initial metal ion concentration (given in units
of mg/L), Ce,i the equilibrium metal ion concentration (also given
in mg/L), and m the adsorbent dose (given in units of g/L).
2.3.3. Analysis of Experimental Data and Prediction of
Performance (Phase 3). The obtained experimental data was
processed with higher-is-better (HB) quality characteristics
(i) to determine the optimum conditions for the adsorption, (ii)
to identify the influence of individual factors on adsorption, and
(iii) to estimate the performance (qtot) under the optimum
conditions. Taguchi defines the loss function L(y) as a quantity
proportional to the deviation from the nominal quality charac-
teristic, and he found the following quadratic form to be a
practical workable function, viz.,
L(y) ) k(y - mT)2 (2)
where k denotes the proportionality constant, mT is the target
value, and y is the experimental value obtained for each trial.
In the case of HB-type quality characteristics, the loss function
Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007 5699
can be written as L(y) ) k(1/y)2 and the expected loss function
can be represented by
E[L(y)] ) kE ()
1
y2
(3)
where E(1/y2) can be estimated from a sample of R as
R
i)1
[1/yi2]
E(1/y2) ) (4)
R
2.3.3.1. Signal-to-Noise (S/N) Ratio. Taguchi created a
transform for the loss function that is called the signal-to-noise
(S/N) ratio, which looks at two characteristics of a distribution
and combines these characteristics into a single number or figure
of merit. The S/N ratio combines the mean level of the quality
characteristic and the variance around this mean into a single
metric.17
A high S/N ratio implies that the signal is much higher than
the random effects of noise factors. Process operation consistent
with the highest S/N ratio always yields optimum quality with
minimum variation.
The S/N ratio consolidates several repetitions (at least two
data points are required) into one value. The equations for
calculating S/N ratios for HB-type characteristics are given as
follows:16
( )
R
1 1
(S/N)HB ) -10 log
R i)1
(5)
yi2
where yi is the value of the characteristic in an observation i
and R is the number of observation or number of repetitions in
a trial. From among the methods suggested by Taguchi for
analyzing the data, the following methods have been used in
the present work: (i) plot of average response curves; (ii)
ANOVA for raw data; and (iii) ANOVA for S/N data.
The plot of the average response at each level of a parameter
indicates the trend. It is a pictorial representation of the effect
of a parameter on the response. The change in the response
characteristic with the change in levels of a parameter can easily
be visualized from these curves. Typically, ANOVA for OAs
is conducted in the same manner as other structured experi-
ments.16 The S/N ratio is treated as a response of the experiment,
which is a measure of the variation within a trial when noise
factors are present. A standard ANOVA can be conducted on
the S/N ratio which will identify the significant parameters
(mean and variation).
2.3.3.2. Prediction of the Mean. After determination of the
optimum condition, the mean of the response () at the optimum
condition is predicted. This mean is estimated only from the
significant parameters. The ANOVA identifies the significant
parameters. Suppose, parameters A and B are significant and
A2, B2 (second level of A ) A2, second level of B ) B2) are
the optimal treatment conditions. The mean under the optimal
condition (optimal value of the response characteristic) then is
estimated as
)T h2 - T
h + (A h ) + (B
h2 - T
h) ) A
h2 + B
h2 - T
h (6)
where Th is the overall mean of the response, and A
h 2 and B
h2
represent average values of response at the second levels of
parameters A and B, respectively.
 5700

Table 2. Column Assignment for the Various Factors and Three Interactions in the Taguchis L27 (313) Orthogonal Array (OA) and Experimental qtot Values for Multicomponent Metal Ions Adsorption
onto BFA
Experimental qtot Values
expt 1, A expt 2, B expt 3, A B expt 4, A B expt 5, C expt 6, A C expt 7, A C expt 8, B C expt 9, D expt 10, E expt 11, B C expt 12, F expt 13, G R1 R2 R3 S/N
ratio (dB)
1 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.00 0.00 0.00
2 0 0 0 0 1 1 1 1 1 1 1 1 1 3.90 4.00 3.86 11.86
3 0 0 0 0 2 2 2 2 2 2 2 2 2 4.25 4.21 4.31 12.58
4 0 1 1 1 0 0 0 1 1 1 2 2 2 2.48 2.36 2.47 7.73
5 0 1 1 1 1 1 1 2 2 2 0 0 0 8.84 8.62 9.25 18.98
6 0 1 1 1 2 2 2 0 0 0 1 1 1 6.99 7.29 6.86 16.95
Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007

7 0 2 2 2 0 0 0 2 2 2 1 1 1 5.78 6.17 5.81 15.44

8 0 2 2 2 1 1 1 0 0 0 2 2 2 4.23 3.83 4.21 12.20
9 0 2 2 2 2 2 2 1 1 1 0 0 0 13.41 13.20 13.38 22.50
10 1 0 1 2 0 1 2 0 1 2 0 1 2 3.29 3.32 3.24 10.33
11 1 0 1 2 1 2 0 1 2 0 1 2 0 3.11 3.22 3.25 10.09
12 1 0 1 2 2 0 1 2 0 1 2 0 1 13.08 12.93 13.36 22.36
13 1 1 2 0 0 1 2 1 2 0 2 0 1 10.00 9.80 10.20 20.00
14 1 1 2 0 1 2 0 2 0 1 0 1 2 4.31 4.06 4.17 12.41
15 1 1 2 0 2 0 1 0 1 2 1 2 0 5.25 5.39 5.13 14.41
16 1 2 0 1 0 1 2 2 0 1 1 2 0 3.52 3.70 3.64 11.17
17 1 2 0 1 1 2 0 0 1 2 2 0 1 11.88 10.30 11.83 21.03
18 1 2 0 1 2 0 1 1 2 0 0 1 2 7.30 6.50 7.15 16.85
19 2 0 2 1 0 2 1 0 2 1 0 2 1 3.55 3.60 3.48 10.98
20 2 0 2 1 1 0 2 1 0 2 1 0 2 12.08 12.74 11.83 21.72
21 2 0 2 1 2 1 0 2 1 0 2 1 0 7.20 7.66 7.84 17.56
22 2 1 0 2 0 2 1 1 0 2 2 1 0 4.31 4.10 4.26 12.51
23 2 1 0 2 1 0 2 2 1 0 0 2 1 4.16 4.05 4.29 12.39
24 2 1 0 2 2 1 0 0 2 1 1 0 2 16.00 14.02 16.08 23.68
25 2 2 1 0 0 2 1 2 1 0 1 0 2 11.08 11.94 11.42 21.19
26 2 2 1 0 1 0 2 0 2 1 2 1 0 7.25 7.36 7.51 17.35
27 2 2 1 0 2 1 0 1 0 2 0 2 1 5.50 6.06 5.36 14.99
total 182.74 180.45 184.18
mean 6.76
 Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007 5701

Table 3. Average and Main Effects of qtot Values for BFA: Raw and S/N Data
Raw Data, Average Value Main Effects (Raw Data) S/N Data, Average Value Main Effects (S/N Data)
L1 L2 L3 L2 - L1 L3 - L2 L1 L2 L3 L2 - L1 L3 - L2
A 5.55 6.78 7.95 1.23 1.18 13.14 15.40 16.93 2.27 1.53
B 5.68 6.84 7.75 1.16 0.91 13.05 15.45 16.97 2.39 1.52
C 4.95 6.60 8.73 1.65 2.13 12.15 15.34 17.99 3.19 2.65
D 6.01 6.98 7.28 0.96 0.31 13.81 15.44 16.22 1.63 0.77
E 6.06 7.43 6.78 1.37 -0.65 14.14 15.56 15.78 1.42 0.22
F 10.64 5.61 4.02 -5.03 -1.59 19.05 14.58 11.84 -4.47 -2.75
G 5.94 7.19 7.14 1.25 -0.05 13.84 16.22 15.41 2.38 -0.81
AB 5.89 7.01 7.38 1.12 0.37 13.71 15.72 16.04 2.01 0.32
AC 6.28 6.88 7.10 0.60 0.22 13.95 15.67 15.85 1.72 0.17
BC 5.96 7.22 7.09 1.26 -0.13 13.69 15.82 15.97 2.13 0.15

2.3.3.3. Determination of Confidence Interval. The estima-
tion of is only a point estimate based on the average of results
obtained from the experiment. Statistically, this provides a 50%
chance of the true average being greater than and a 50%
chance of the true average being less than . Therefore, it is
customary to represent the values of a statistical parameter as
a range within which it is likely to fall for a given level of
confidence. This range is termed as the confidence interval (CI).
In other words, the confidence interval is a maximum and
minimum value between which the true average should fall at
some stated percentage of confidence.
The following two types of confidence intervals are suggested
by Taguchi, in regard to the estimated mean of the optimal
treatment condition:16
(i) Around the estimated average of a treatment condition
predicted from the experiment. This type of confidence interval
is designated as CIPOP (confidence interval for the population).
(ii) Around the estimated average of a treatment condition
used in a confirmation experiment to verify predictions. This
type of confidence interval is designated as CICE (confidence
interval for a sample group).
The difference between CIPOP and CICE is that CIPOP is
associated with the entire population, i.e., all parts ever made
under the specified conditions, and CICE is associated with
only a sample group made under the specified conditions.
Because of the smaller size (in confirmation experiments),
relative to the entire population, CICE must be slightly wider.
The expressions for computing the confidence interval are given
as follows:18
2.3.4. Confirmation Experiment (Phase 4). The confirma-
tion experiment is the final step in verifying the conclusions
drawn from the previous round of experimentation. The
optimum conditions are set for the significant parameters (the
insignificant parameters are set at economic levels), and a
selected number of tests are conducted under constant specified
conditions. The average of the results of the confirmation
experiments is compared with the anticipated average, based
on the parameters and levels tested. The confirmation experiment
is a crucial step and is highly recommended to verify the
experimental conclusions.
3. Results and Discussion
Experiments were conducted for Cd(II), Ni(II), and Zn(II)
ion adsorption onto BFA, according to the test conditions
specified by L27 OA (see Table 2). Each experiment was
repeated three times for each trial condition. The average or
mean values of qtot and S/N ratio for each parameter at levels
1, 2, and 3 are calculated from Table 2. It is observed that metal
adsorption is strongly dependent on the parametric conditions.
3.1. Effect of Process Parameters. The raw data for the
average value of qtot and S/N ratio for each parameter at levels
1, 2, and 3, along with interactions at the assigned levels, are
given in Table 3 for metal adsorption onto BFA. Various metal
removal parameters (C0,i, T, pH0, m, and t) significantly affect
the qtot values. The interaction effect of concentration of one
metal ion with respect to (wrt) another metal ion also has
significant influence on the qtot values. Individually, relative to
the level stage, with qtot as the desired response characteristic,
m (parameter F) has the highest influence at level 1, pH0

x
FR(1,fe)Ve (parameter E) has the highest influence at level 2, and C0,Zn
CIPOP ) (7) (parameter C) has the highest influence at level 3. The difference
neff
between level 2 and level 1 (L2 - L1) of each factor indicates

x [ ]
1 1 the relative influence of the effect. The larger the difference,
CICE ) FR(1,fe)Ve + (8) the stronger the influence. Table 3 shows that no single
neff R
parameter has an overriding or predominant influence over
others for the removal of Cd(II), Ni(II), and Zn(II) from aqueous
where FR(1, fe) represents the F-ratio at a confidence level of
solution by BFA. C0,i shows a stronger influence on qtot than
(1 - R) against DOF ) 1 and a DOF error of fe, Ve is the error
that of other parameters. The qtot value increased as C0,i
variance (from ANOVA), and neff is defined as
increased, because the resistance to the metal uptake decreased
as the mass-transfer driving force increased.
neff )
The response curves for the individual effects of metal
N adsorption parameters on the average value of qtot and respective
(9)
1 + [total DOF associated in the estimate of the mean] S/N ratio for metal adsorption onto BFA are given in Figure 1.
An increase in the levels of factors such as C0,i, and T, from 1
where N is the total number of results. R represents the sample to 2 and from 2 to 3, has resulted in an increase in the qtot values.
size for the confirmation experiment. Because sorption is an exothermic process, it would be
Equation 8 shows that, as R approaches infinity (i.e., the entire expected that an increase in T would result in a decrease in the
population), the value 1/R approaches zero and CICE ) CIPOP. qtot value. However, if the diffusion process controls the
As R approaches 1, CICE becomes wider. adsorption process, the qtot value will increase as T increases,
5702 Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007
Figure 1. Effect of process parameters on qtot and S/N ratio for multicomponent adsorption of metal ions onto BFA.
because of the endothermicity of the diffusion process. An
increase in T results in increased mobility of the metal ions
and a decrease in the retarding forces acting on the diffusing
ions. These result in the enhancement in the sorptive capacity
of the adsorbents. However, the diffusion of the metal ions into
the pores of the adsorbent is not the only rate-controlling step,12
and the diffusion resistance can be ignored with adequate contact
time. Therefore, the increase in sorptive uptake of the metal
ions with an increase in temperature may be attributed to
chemisorption.
An increase in the level of contact time t, from 1 to 2, results
in an increase in the qtot value. However, the qtot value remains
constant with a subsequent increase from level 2 to level 3.
Also, the adsorption of metal ions increases as t increases until
equilibrium is attained between the solute molecules in the liquid
and the solid phases. During the initial stage of sorption, a large
number of vacant surface sites are available for adsorption. As
the sorption process progresses, its intention is to occupy the
vacant sites, because of the repulsive forces between the solute
molecules onto the solid surface and the bulk liquid phase.
Besides, the metal ions are adsorbed into the mesopores that
get almost saturated with metal ions during the initial stage of
adsorption. Thereafter, the metal ions must traverse farther and
deeper into the pores, encountering much-greater resistance. This
results in the slowing of the adsorption during the later period
of adsorption.19
An increase in pH0 has resulted in higher adsorption up to
level 2 and subsequent increase resulted in the decrease in the
desired characteristic (qtot). The removal of metal ions is
determined to increase as pH0 increases from 4 to 6. The
maximum uptake of metal ions was obtained at pH0 6, and
the qtot value decreased at pH0 >6. The oxides of aluminum,
calcium and silicon present in the BFA develop charges when
in contact with water. Except silica, all other oxides possess a
positive charge for the pH range of interest, because the zero-
point charge (pHZPC) of SiO2, Fe2O3, Al2O3, and CaO are 2.2,
6.7, 8.5, and 11.0, respectively.20 A positive charge develops
on the surface of the oxides of BFA in an acidic medium,
because of the aqua complex formation of the oxides present,
as follows:
H+
-MO + H-OH 98 M-OH2+ + OH- (10)
Metal-ion adsorption at low pH0 ( pH0 e6) is less than that
at higher pH0 (6). This is due to the fact that the surface charge
that is developed at low pH0 is not suitable for the adsorption
of these metal ions. For pH0 <6, a significant electrostatic
repulsion exists between the positively charged surface of the
BFA and the cationic metal ions. Besides, a higher concentration
of H+ in the solution competes with metal ions for the adsorption
sites, resulting in the reduced uptake of metal ions.
As the pH0 of the system increases, the number of positively
charged sites decreases and the number of negatively charged
sites increases on the surface of BFA, as shown below:
-MOH + OH- f -MO- + H2O (11)
-MO- + Cd f s M-O-Cd (12)
A negatively charged surface site on the BFA favors the
adsorption of cationic metal ions, because of electrostatic
attraction.9,10
A pH0 value of 8 is supposed to be more favorable to increase
the qtot value; on the contrary, the qtot value decreases at pH0 8.
It is known that metal species [M(II) ) Cd(II), Ni(II), and Zn-
(II)] are present in deionized water in the forms of M2+,
M(OH)+, M(OH)20, M(OH)2(S), etc.21 At pH 4.0, the solubility
(CT,M) of the M(OH)2(S) is great, so M2+ is the main species.
At pH 8.0, the CT,M value for M(OH)2(S) is much smaller.
With the increase of the pH value, the CT,M value for M(OH)2(S)
decreases further. In the alkaline region, therefore, the main
species in the solution is M(OH)2(S), which is electrically neutral.
Hence, in the alkaline region, the removal of cationic metal ions
is not due to electrostatic attraction but rather precipitation.
Because Cd(II), Ni(II), and Zn(II) ions are simultaneously being
removed, because of some complex mechanism, the qtot value
decreases.
In the case of m, an increase in m from level 1 to level 2 and
subsequently to level 3 led to a decrease in the value of qtot.
Mall et al.6 showed the that unit adsorption decreases as m
increases, although the percentage metal removal increases,
because of the availability of a greater surface area and more
adsorption sites.22
Table 3 indicates that the interactions between initial con-
centrations of Cd(II), Ni(II), and Zn(II) metal ions [(A B),

Figure 2. Interaction between parameters A, B, and C at three levels on qtot and S/N ratio for multicomponent adsorption of metal ions onto BFA.
(A C), or (B C)] are significant in regard to affecting the
average value of qtot. These interaction graphs are shown in
Figure 2 for qtot values, along with the S/N ratios, for metal
adsorption onto BFA.
If the lines are parallel in the interaction graph, then it implies
that there is no interaction between the factors. Nonparallel lines
in the interaction plot indicate the existence of an interaction
between the factors. According to Taguchi,18 the greater the
difference between the slopes of the lines of two factors in the
range tested, the greater the interaction.
Figure 2 shows that the difference in the slopes of the lines
is greater when the level of the parameters is lower. Hence, it
may be concluded that the effect of the initial concentration of
metal ions on qtot is more pronounced when the C0 value of
metal ions is increased from the lowest level to the middle level,
as compared to that when C0 is increased from the middle level
to the highest level.
Srivastava et al.9,10 have shown that the mutual effect of one
metal ion on the adsorption of another metal ion is antagonistic
in nature. The most logical reason for the antagonistic action is
claimed to be the competition between the adsorbate ions to
occupy vacant adsorption sites on the adsorbents. It appears that
Cd(II), Ni(II), and Zn(II) metal ions share the binding sites on
the surface of adsorbents, and, therefore, the adsorption of one
Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007 5703
metal ion decreases the number of binding sites available for
the adsorption of other metal ions. This ultimately leads to the
antagonism behavior. The screening effect may be another
possible explanation for the observed antagonism. The increas-
ing concentrations of metal ions that are not adsorbed can mask
preferentially adsorbed metal ions.
At lower initial metal concentrations, the antagonistic nature
is least observed. Therefore, when the initial concentration is
increased from the lowest level to the next higher level, qtot
values show the highest incremental rate. When the initial
concentration is further increased, this rate of increment of qtot
decreases for the adsorption of Cd(II), Ni(II), and Zn(II) metal
ions by BFA.
The contribution of individual factors is the key for the control
to be enforced for the adsorption of various metal ions onto
BFA. ANOVA results for raw and S/N ratio data with desired
response characteristics (qtot) are given in Table 4 for multi-
component metal ion adsorption onto BFA. From the calculated
ratios (F), it can be referred that all factors and interactions
considered in the experimental design with qtot as the desired
response characteristic are statistically significant at the 95%
confidence limit.
5704 Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007

Figure 3. Percent contribution of various parameters for qtot for multicomponent adsorption of metal ions onto BFA: parameter A, C0,Cd (mg/L); parameter
B, C0,Ni (mg/L); parameter C, C0,Zn (mg/L); parameter D, T (C); parameter E, pH0; parameter F, m (g/L); and parameter G, t (min).

Table 4. ANOVA of qtot and S/N Ratio Data for Multicomponent Adsorption of Metal Ions onto BFA
Raw Data S/N Data
parameter sum of squares DOFa mean square % contribution F-value sum of squares DOFa mean square % contribution F-value
A 78.25 2 39.13 6.45 305.47 65.50 2 32.75 8.58 4.58
B 58.36 2 29.18 4.81 227.82 70.07 2 35.03 9.18 4.90
C 194.44 2 97.22 16.04 759.03 153.74 2 76.87 20.14 10.75
D 23.63 2 11.81 1.95 92.23 27.11 2 13.55 3.55 1.90
E 25.52 2 12.76 2.10 99.60 (14.30) (2) (7.15) POOLED
F 644.37 2 322.19 53.14 2515.43 238.54 2 119.27 31.25 16.68
G 27.01 2 13.51 2.23 105.46 26.38 2 13.19 3.46 1.84
AB 65.85 4 16.46 5.43 128.53 59.96 4 14.99 7.85 2.10
AC 21.36 4 5.34 1.76 41.70 42.21 4 10.55 5.53 1.48
BC 66.87 4 16.72 5.52 130.53 65.57 4 16.39 8.59 2.29
residual 6.92 54 0.13 0.57 14.30 2 7.15 1.87
model 1205.67 26 564.18 99.43 4404.79 763.39 24 332.61 98.13 46.52
cor. total 1212.59 80 564.31 100.00 777.69 26 339.76 100.00
a Degrees of freedom.

Table 5. Predicted Optimal qtot Values, Confidence Intervals, and Results of Confirmation Experiments
optimal levels of predicted optimal confidence average of confirmation
adsorbent process parameters values (mg/g) intervals (95%) experiments (mg/g)
BFA A3, B3, C3, D3, E2, F1, G2 16.41 CIPOP: 16.00 < BFA < 16.82 16.01
CICE: 15.88 < BFA < 16.94

By studying the main effects of each of the factors, the general
trends of the influence of the factors on the adsorptive metal
removal process can be characterized. The characteristics can
be controlled such that a lower or higher value in a particular
influencing factor produces the preferred result. Thus, the levels
of factors necessary to produce the best results can be predicted.
The percentage contribution of each parameter, for qtot as the
desired response characteristic, is shown in Figure 3. Table 4
shows that parameter F (m) is the most significant factor with
53.14% and 31.25% contribution to the raw and S/N ratio
data for the metal adsorption with qtot as the desired character-
istic within the assigned levels for each factor. It can also be
observed from Table 4 and Figure 3 that the interactions between
the parameters A, B, and C contribute significantly to both raw
and S/N ratio data for simultaneous metal removal onto BFA.
3.2. Selection of Optimal Levels and Estimation of
Optimum Response Characteristics. Because qtot is an HB-
type quality characteristic, the greater qtot value is considered
optimal. Table 5 summarizes the optimal level of various
parameters obtained after examining the response curves (Figure
1) of the average value of qtot and S/N ratios for metal adsorption
onto BFA. Table 5 indicates that the first level of parameter F
(m), the second level of parameters E (pH0) and G (t), and the
third levels of parameters A, B, C (C0,i), and D (temperature)
have higher average values of qtot and S/N ratio. Because the
intent of the work is to remove the maximum amount of metals
with the highest possible concentration of Cd(II), Ni(II), and
Zn(II) metal ions present together, the third levels of parameters
A, B, and C (C0,Cd, C0,Ni, and C0,Zn) are suggested for further
calculations.
Thus, the significant process parameters that affect the metal
removal by BFA and their optimal levels (as already selected)
are A3, B3, C3, D3, E2, F1, and G2.
 Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007 5705

The average qtot values (from Table 3) are given as large number of variables spanned by factors and their settings
with a small number of experiments. Factors such as initial
h 3) ) 7.95
third level of concentration of Cd(II) ion (A metal-ion concentration, temperature, pH0, adsorbent dose, and
contact time at three levels with a OA layout of L27 (313) could
h 3) ) 7.75
third level of concentration of Ni(II) ion (B be optimized with the higher-is-better-type quality charac-
h 3) ) 8.73
third level of concentration of Zn(II) ion (C teristics with 27 sets of experiments only. The interactions
between initial concentrations of Cd(II), Ni(II), and Zn(II) metal
h 3) ) 7.28
third level of temperature (D ions [(A B), (A C) or (B C)] is significant in affecting
the average values of qtot. The effect of initial concentration of
h 2) ) 7.43
second level of pH0 (E one metal ion (C0,Cd or C0,Ni) on qtot values is more pronounced
at the lower concentration of the other metal ions (C0,Ni or C0,Zn)
h 1) ) 10.64
first level of adsorbent dosage (F
for all possible interactions. All factors and interactions
h 2) ) 7.19
second level of contact time (G considered in the experimental design with qtot as the desired
response characteristic are statistically significant at the 95%
h BFA) is 6.76 (from Table 2).
The overall mean of qtot (T confidence limit.
The predicted optimum value of qtot for BFA (BFA) has been
calculated as Literature Cited

BFA ) T
h BFA + (Ah3 - T
h BFA) + (Bh3 - T
h BFA) + (1) Standards for Pollution Control; Central Pollution Control Board
(CPCB), Government of India, Delhi, 2002.
h3 - T
(C h BFA) + (Dh3 - T
h BFA) + (Eh2 - Th BFA) + (2) Palmer, S. A. K.; Breton, M. A.; Nunno, T. J.; Sullivan, D. M.;
h1 - T
(F h BFA) + (Gh2 - T
h BFA) Norman, F. Surprenant Technical Resource Document: Treatment Tech-
nologies for Metal/Cyanide-Containing Wastes, Volume III. United States
) 16.41 mg/g Environmental Protection E Agency. Feb. 1988, EPA/60O/S2-87/106.
(3) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Treatment of pulp and
The 95% confidence intervals for the mean of the population paper mill wastewaters with polyaluminium chloride and bagasse flyash.
Colloids Surf. A 2005, 260, 17.
and three confirmation experiments (CIPOP and CICE) is calcu- (4) Srivastava, V. C.; Swamy, M. M.; Mall, I. D.; Prasad, B.; Mishra,
lated by substituting the total number of results (N ) 27 3 ) I. M. Adsorptive removal of phenol by bagasse fly ash and activated
81), the DOF error (fe ) (80 - 26) ) 54), and the error variance carbon: equilibrium, kinetics and thermodynamic study. Colloids Surf. A
(Ve ) 0.128) (recalculated from Table 4) into eqs 7-9: 2006, 272, 89.
(5) Lataye, D. H.; Mishra, I. M.; Mall, I. D. Removal of pyridine from
neff ) aqueous solution by adsorption on bagasse fly ash. Ind. Eng. Chem. Res.
2006, 45, 3934.
N
)3 (6) Mall, I. D.; Srivastava, V. C.; Agarwal, N. K.; Mishra, I. M.
1 + [total DOF associated in the estimate of the mean] Adsorptive removal of malachite green dye from aqueous solution by
bagasse fly ash and activated carbon-kinetic study and equilibrium isotherm
F0.05(1, 54) ) 4.03 (tabulated F-value) analyses. Colloids Surf. A 2005, 264, 17.
(7) Mall, I. D.; Srivastava, V. C.; Agarwal, N. K.; Mishra, I. M. Removal
of congo red from aqueous solution by bagasse fly ash and activated

x
FR(1,fe)Ve carbon: kinetic study and equilibrium isotherm analyses. Chemosphere
CIPOP ) ) (0.41 2005, 61, 492.
neff (8) Mall, I. D.; Srivastava, V. C.; Agarwal, N. K. Removal of orange-G
and methyl violet dyes by adsorption onto bagasse fly ash-kinetic study

x [ ]
1 1
CICE ) FR(1,fe)Ve + ) (0.53
neff R
The 95% confidence intervals (CIPOP and CICE) of the predicted
ranges of qtot for the simultaneous adsorption of Cd(II), Ni(II),
and Zn(II) ions onto BFA are given in Table 5.
3.3. Confirmation Experiments. Three confirmation experi-
ments have been conducted for the simultaneous adsorption of
Cd(II), Ni(II), and Zn(II) ions onto BFA at selected optimal
levels of the process parameters. The average values of the
characteristics are obtained and compared with the predicted
values. The results are given in Table 5. The values of qtot
obtained through the confirmation experiments are within 95%
of CICE. Note that these optimal values are valid within the
specified range of process parameters; any extrapolation/
interpolation should be confirmed through additional experi-
ments.
4. Conclusions
The Taguchi orthogonal array (OA) design of experiments
(DOE) methodology was determined to be very economical in
the experimental sorption studies of Cd(II), Ni(II), and Zn(II)
metal ions from aqueous solutions by bagasse fly ash (BFA).
This approach facilitated understanding of the interaction of a
and equilibrium isotherm analyses. Dyes Pigm. 2006, 69, 210.
(9) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Equilibrium modelling
of single and binary adsorption of cadmium and nickel onto bagasse fly
ash. Chem. Eng. J. 2006, 117, 79.
(10) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Modelling individual
and competitive adsorption of Cadmium(II) and Zinc(II) metal ions from
aqueous solution onto bagasse fly ash. Sep. Sci. Technol. 2006, 41, 2685.
(11) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Competitive antagonistic
adsorption of nickel(II) and zinc(II) metal ions from aqueous solution onto
bagasse fly ash. Presented at the 11th APCChE Congress, Asian Pacific
Confederation of Chemical Engineering, Kuala Lumpur, Malaysia, August
27-30, 2006.
(12) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Adsorption thermo-
dynamics and isosteric heat of adsorption of toxic metal ions onto bagasse
fly ash (BFA) and rice husk ash (RHA). Chem. Eng. J. 2007, 132, 267-
278.
(13) Taguchi, G. Introduction to Quality Engineering: Designing Quality
into Products and Processes; Asian Productivity Organization: Tokyo, 1986.
(14) Taguchi, G.; Wu, Y.-i. Introduction to Off-line Quality Control;
Central Japan Quality Control Association: Nagoya, Japan, 1979.
(15) Byrne, D. M.; Taguchi, S. The Taguchi Approach to Parameter
Design. Qual. Progress 1987, (December), 19.
(16) Ross, P. J. Taguchi Techniques for Quality Engineering: Loss
Function, Orthogonal Experiments, Parameter and Tolerance Design, 2nd
Edition; McGraw-Hill: New York, 1996.
(17) Barker, T. B. Engineering Quality by Design: Interpreting the
Taguchi Approach; Marcel Dekker: New York, 1990.
(18) Roy, R. K. A Primer on the Taguchi Method; Society of
Manufacturing Engineers: Dearborn, MI, 1990.
5706 Ind. Eng. Chem. Res., Vol. 46, No. 17, 2007
(19) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Characterization of
mesoporous rice husk ash (RHA) and adsorption kinetics of metal ions from
aqueous solution onto RHA. J. Hazard. Mater. 2006, B134, 257-267.
(20) Panday, K. K.; Prasad, G.; Singh, V. N. Mixed adsorbent for Cu-
(II) removal from aqueous solutions. EnViron. Technol. Lett. 1986, 50 (7),
547.
(21) Srivastava, V. C.; Mall, I. D.; Mishra, I. M. Adsorption of toxic
metal ions onto activated carbon. Study of sorption behaviour through
characterization and kinetics. Chem. Eng. Process. 2007, doi:10.1016/
j.cep.2007.04.006.
(22) Ponnusami, V.; Krithika, V.; Madhuram, R.; Srivastava, S. N.;
Biosorption of reactive dye using acid-treated rice husk: Factorial design
analysis. J. Hazard. Mater. 2007, 142, 397.
ReceiVed for reView July 27, 2006
ReVised manuscript receiVed May 17, 2007
Accepted May 22, 2007
IE0609822