464 © IWA Publishing 2014 Water Science & Technology | 69.

3 | 2014

The use of response surface methodology for modelling

and analysis of water and wastewater treatment
processes: a review
Abhilash T. Nair, Abhipsa R. Makwana and M. Mansoor Ahammed

ABSTRACT
Abhilash T. Nair
In recent years, response surface methodology (RSM) has been used for modelling and optimising a
Abhipsa R. Makwana
variety of water and wastewater treatment processes. RSM is a collection of mathematical and M. Mansoor Ahammed (corresponding author)
Department of Civil Engineering,
statistical techniques for building models, evaluating the effects of several variables, and obtaining S V National Institute of Technology,
Surat – 395007,
the values of process variables that produce desirable values of the response. This paper reviews India
E-mail: mansoorahammed@gmail.com
the recent information on the use of RSM in different water and wastewater treatment processes.
The theoretical principles and steps for its application are first described. The recent investigations
on its application in coagulation–flocculation, adsorption, advanced oxidation processes, electro-
chemical processes and disinfection are reviewed. The limitations of the methodology are
highlighted. Attempts made to improve the RSM by combining it with other modelling techniques are
also described.
Key words | experimental design, optimisation, response surface methodology (RSM), wastewater
treatment, water treatment

INTRODUCTION

The efficiency of different processes employed in water and
wastewater treatment are influenced by a number of process
variables. Optimisation of these processes in order to obtain
the maximum benefit would result in both cost reduction as
well as reduction in consumption of valuable resources such
as energy and materials. The traditional approach to the
optimisation problem is the one-factor-at-time method. In
this approach, the influence of one variable is studied
while keeping other variables at a constant level. In order
to obtain the optimum conditions, this procedure is repeated
with other variables also. This approach, however, does not
depict the interactive effects among the variables studied,
and thus cannot give the complete effects of the variables
on the process. Further, the number of experiments required
in the one-factor-at-time approach would be large, thus
making it costly and time consuming (Mason et al. ).
Design of experiments has been used to overcome these
problems. The advantages of the design of experiments
include the same amount of information in fewer exper-
iments, estimation of interactions between the factors and
development of empirical models. The graphical perspective
of the design of experiments has led to the response surface
doi: 10.2166/wst.2013.733
methodology (RSM) (Ankenman & Dean ; Myers et al.
; Montgomery ). RSM is a collection of mathemat-
ical and statistical techniques for the design of
experiments, building models, evaluating the effects of sev-
eral factors, and obtaining the optimum conditions for
responses with a limited number of planned experiments
(Khuri & Cornell ). Originally developed by Box and
Wilson (Box & Wilson ) to improve yield from chemical
and other process industries, RSM now finds application in
varied fields such as electronics, biotechnology, aerospace,
automotive, life sciences, agricultural settings and process
industries (Anderson-Cook et al. ; Myers et al. ).
In recent years RSM has become a popular tool for opti-
mising and analysing different water and wastewater
treatment processes such as coagulation–flocculation,
adsorption, advanced oxidation processes, electro-chemical
processes and disinfection. Availability of several computer
softwares specifically for RSM has made the task of applying
RSM rather simple. However, this has also led to the use of
RSM in situations where it is not useful/relevant. A
thorough understanding of the RSM including its limit-
ations/applicability as well as the process being studied is

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 465 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes
needed for successful application of this methodology. This
paper reviews the recent literature on the use of RSM in
different water and wastewater treatment processes. The
basic procedure of RSM is first described. Its applications
in coagulation–flocculation, adsorption, advanced oxidation
processes, electro-chemical processes, disinfection, etc. are
reviewed. The limitations of RSM are also highlighted.
Attempts made to improve the RSM by combining it with
other techniques are also described.
RSM PROCEDURE
In RSM, mathematical models generated by using data on
experimental design, defines the relationships between the
independent variables (factors) and the dependent variables
(responses). These models are used in analysing the effects
of independent variables and their interactions on the
responses, and also for optimising the process. The results
are generally presented as 2-D contours and 3-D plots. The
RSM requires the use of statistical experimental design,
linear regression modelling and optimisation methods. Sev-
eral stages/steps are involved in the application of RSM as
an optimisation tool. These include (i) selection of indepen-
dent variables and their ranges, (ii) selection of experimental
design and carrying out the experiments, (iii) generation of
linear regression model equation based on the experimental
results, (iv) verification of model adequacy and (v) graphical
representation of the model and obtaining optimal
conditions.
Selection of independent variables
A large number of independent variables (factors) may affect
the response of a system. Since it is not possible to include
all these variables in the experimental design due to econ-
omic reasons, screening experiments are necessary to
identify the variables with major effects. These variables
are generally identified by conducting experiments with
the one-factor-at-a-time approach or with two-level factorial
designs (Montgomery ). Selection of proper range
(level) for these factors over which the variables are to be
tested is also important since it affects the accuracy of the
model equation. Prior knowledge of the system/process
being studied is crucial to select a narrower range for the
factors.
Codification of selected variables is done before
regression analysis. Codification is done in order to normal-
ise the variables. Independent variables may have different
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Water Science & Technology | 69.3 | 2014
units and orders of magnitude, and codification ensures
that all independent variables affect the responses evenly.
The following equation can be used to transform a real
value into a coded value (Moghaddam et al. ):
zi  z0
xi ¼ (1)
Δzi
where xi ¼ dimensionless coded value of independent vari-
able, zi ¼ uncoded value of the ith independent variable,
z0 ¼ uncoded ith independent variable at the centre point,
the Δzi ¼ step change value between the low level (1)
and high level (þ1) (Moghaddam et al. ).
Experimental design
Different designs are available for conducting the exper-
iments. These designs differ from one another with respect
to their selection of experimental points and number of
runs. Some of the popularly used experimental designs are
(i) full three-level factorial design, (ii) Box–Behnken design
(BBD) and (iii) central composite design (CCD). Experimen-
tal design matrices for these designs for three independent
variables are presented in Figure 1.
In full three-level factorial design the factors are varied
at three levels, 1, 0 and þ1 representing minimum, mean
and maximum respectively. The number of experiments
required is 3k where k is the number of independent vari-
ables. For more than two independent variables, the
number of experiments required for full three-level factorial
design becomes very large, and other designs are generally
used.
Proposed by Box and Behnken in 1960, the Box–Behn-
ken design is formed by combining two-level factorial design
with incomplete block design (Box & Behnken ; Khuri
& Cornell ). In BBD all experimental points lie on a
sphere of radius √2 and BBD is usually very efficient due
Figure 1 | Different experimental designs for three variables (k ¼ 3) (a) three-level full
factorial design (n ¼ 27), (b) Box–Behnken design (n ¼ 15) and (c) central
composite design (n ¼ 17). n ¼ number of experiments with cp ¼ 1 for (a) while
cp ¼ 3 for (b) and (c). ( ) Factorial design points, ( ) central points and ( )
axial points.
 466 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes
to reduced number of runs as compared with full factorial
design, as shown in Figure 1(b). As Box–Behnken design
does not contain any experimental points at the vertices of
the cubic region, this could be advantageous when testing
at these points is expensive or impossible due to practical
reasons (Montgomery ). The number of experiments is
governed by the expression 2k (k–1) þ cp, where k is the
number of factors and cp is the number of replicates at the
central point (Bezerra et al. ).
Central composite design was introduced by Box and
Wilson in 1951 as an alternative to full-level factorial
design (Box & Wilson ). Central composite design
consists of a two-level factorial design, a central point
and an additional design in which experimental points
are at a distance α from the centre. The number of exper-
imental runs can be calculated from the expression 2k þ
2k þ cp where cp is the number of replicates at the central
point. The value of α is generally taken as α ¼ √k
(Montgomery ). Central composite design gives quite
high efficiency for up to about five or six factors and
then begins to decrease rapidly. CCD can be applied for
optimisation with a large number of factors if all the
experiments can be carried out in parallel (i.e. all at
the same time) instead of sequentially (i.e. one after the
other) (Massart et al. ). Although designs such as
the Doehlert uniform shell design, Box–Draper saturated
designs and D-optimal designs are described in the litera-
ture, these designs are rarely used in the field of water and
wastewater treatment as central composite design and
Box–Behnken design are simpler and robust. Doehlert
designs are not rotatable while central composite designs
are rotatable (Montgomery ). Central composite
designs consist of factorial and axial points which help
in sequential strategy of experimentation. If curvature is
important, the two-level design can be augumented with
axial runs to obtain central composite design (Montgom-
ery ). Box–Behnken designs are economical and
hence popular in industrial research.
Selection of model
In most RSM problems, since the form of the relationship
between independent variables and response is unknown,
suitable approximation between the factors and response
is to be found. The most widely used approximating func-
tions are polynomials. Since a simple linear equation
cannot describe the interaction effect between different par-
ameters and cannot determine the critical point, the full
quadratic second-order equation (Equation (2)) with
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Water Science & Technology | 69.3 | 2014
interaction terms is generally used in RSM.
X
k X
k X
k¼1 X
k
y ¼ β0 þ β i xi þ β ii x2i þ β ij xi xj þ ε (2)
i¼1 i¼1 i¼1 j¼iþ1
where β0, βi, βii and βij are regression coefficients for inter-
cept, linear, quadratic and interaction coefficients
respectively, xi and xj are coded independent variables and
ε is the residuals associated to the experiments. This
model can evaluate the interactive effects between different
independent variables and the critical point (maximum,
minimum or saddle points).
Model adequacy checking
Once a suitable mathematical model has been chosen, the
predictive ability of the model should be validated before
it is used for prediction. This is to ensure that the model pro-
vides an adequate approximation to the true system.
Different expressions used for this checking are summarised
in Table 1. The overall efficiency of a model prediction is
generally explained by coefficient of determination (R 2).
R 2 is the ratio of regression sum of squares to total sum of
squares (Table 1), and it measures the total variation of pre-
dicted or model values from the mean. For a model with
good prediction efficiency, the value of R 2 should be close
to 1.0. The model prediction efficiency, however, should
not be assessed by R 2 alone (Sarabia & Ortiz ;
Montgomery ) since R 2 increases with the increase in
the number of terms in the model, irrespective of its statisti-
cal significance. R 2 value should be compared with adjusted
R 2 which reflects the number of factors in the experiment
(Montgomery ). R 2adjusted value often decreases if statisti-
cally insignificant variables are added. When R 2 and
R 2adjusted differ dramatically, there is a good chance that
non-significant terms have been included in the model (Sar-
abia & Ortiz ; Montgomery ). The difference
between the predicted and the actual value is termed as
residual and it plays an important role in judging model ade-
quacy. Another statistic used for measuring the predictive
ability of a model is the prediction error sum of squares
(PRESS) (Table 1). It is a measure of how well the model
for the experiment is likely to predict the response in a
new experiment. Small values of PRESS are desirable
(Montgomery ). R 2predicted which describes the prediction
capability of the model for new responses can be calculated
from PRESS. R 2 and R 2predicted should be in close agreement
with each other (Myers et al. ).
 467 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes Water Science & Technology | 69.3 | 2014

Table 1 | Expressions used for model adequacy verification

Terms Expressions Remarks

SSRes
Coefficient of R2 ¼ R 2 should be close to 1.0
SST
determination
SSRes =ðn  pÞ
R 2adjusted R2adjusted ¼ 1  R 2adjusted should be close to 1.0
SST =ðn  1Þ
P
n
2
Prediction error sum of PRESS ¼ [yi  ^yi ] PRESS should have a small value
i¼1
square (PRESS)
PRESS
R 2predicted R2predicted ¼ 1  R 2predicted should not have difference of more than 0.2 with R 2adjusted
SST
Mean square of model
Significance of regression F0 ¼ This ratio should be larger than the tabulated F value for a good model
Mean square of residual
SSLOF =ð f  pÞ
Lack of Fit (LOF) test FLOF ¼ This ratio should be lower than the tabulated F value for a good model
SSPE =ðn  pÞ

SSRes ¼ sum of square of error; SST ¼ total sum of squares; n ¼ number of experiments in the set; f ¼ number of distinctly different factor combinations; p ¼ number of parameters in the
model; yi ¼ observed value; ŷi ¼ predicted value.
Adapted from Myers et al. (2009); Sarabia & Ortiz (2009); Montgomery (2010).

The significance of each factor and interactions between
each other is checked with the help of a Fisher test. The larger
the magnitude of the F-value and correspondingly the smaller
the ‘p > F’, the more significant are the corresponding model
and the individual coefficients (Montgomery ). If ‘p > F’
value is below 0.05, then the model is significant at 95% con-
fidence interval. The model can also be evaluated by the lack
of fit test. The lack of fit test measures the model failure in
representing data points in the experimental domain by com-
paring the residual error to the pure error from the replicated
experimental design points (generally the central points in
the experimental design) and should be insignificant. If this
ratio is greater than the tabulated F value, it is concluded
that there is evidence of a lack of fit and the model needs
improvement (Massart et al. ).
Normal probability plot of residuals is constructed in
order to check the normality assumption. If the residuals
are normally distributed, the plot of the residuals will
follow a straight line with some moderate scatter indicating
that the model is well fitted. (Carlson & Carlson ;
Anderson & Whitcomb ). Plot of experimental response
values versus the predicted response values also helps to
evaluate the model. The points should be split evenly
W
along the 45 line. Groups of points above or below the
line indicate areas of over or under prediction (Anderson
& Whitcomb ).
Graphical representation of the model
In RSM the visualisation of the regression model can be
obtained by surface response plots and contour plots. The
three dimensional graphical representation of the fitted
models is termed a response surface while the two dimen-
sional plot is known as a contour plot. These graphical
plots are helpful to understand the nature of the response
at different factor levels.
Figure 2 presents different profiles for the quadratic
response surface plots in the optimisation of two variables
based on Equation (2). Figures 2(a) and 2(b) represent sur-
faces where the maximum and minimum points are within
the experimental region and the contour plots display
ellipses or circles. When a contour plot displays a hyperbolic
system, as in Figure 2(c), it presents a saddle point which is
an inflexion point between a relative maximum and relative
minimum and it is neither a minimum nor a maximum
point. Figure 2(d) shows that the maximum point is outside
the experimental region, while in Figure 2(e) there is a pla-
teau in relation to a variable and variation of its level will
not affect the system. It may be noted that if there are
three or more factors, the plot visualisation is possible
only if one or more variables are set to a constant value.
Response surface optimisation
Response surfaces can be analysed to obtain the maximum
or minimum responses and the corresponding optimum
conditions. With multiple responses, the optimum con-
ditions can be met when all the parameters concurrently
meet the desirable criteria. The optimum conditions can
be obtained graphically by superimposing the contours of
the response surfaces of the regression models in an overlay
plot. Graphical optimisation displays the area of feasible

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 468 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes
Figure 2 | Different profiles of surface response plots and the corresponding contour plots from a quadratic model: (a) maximum, (b) minimum, (c) saddle, (d) maximum outside the
experimental region and (e) plateau.
response values in the factor space and the regions that fit
the optimisation criteria (Ghafari et al. ).
When there are more than three independent variables
it will be difficult to find the conditions that simultaneously
satisfy all the responses (Myers et al. ; Montgomery
). Here the use of multicriteria methodology can be fol-
lowed. Desirability function is the mostly commonly used
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Water Science & Technology | 69.3 | 2014
multicriteria methodology. In this, each response is con-
verted into an individual desirability function that varies
over the range 0 to 1. If the response is at its target,
then desirability function is 1, and if a response is outside
an acceptable region, then the desirability functions is
0. The simultaneous optimisation process is reduced to
find the levels of factors that give the maximum overall
 469 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes
desirability (Bezerra et al. ; Myers et al. ; Mont-
gomery ).
APPLICATIONS OF RSM IN WATER AND
WASTEWATER TREATMENT
In recent years a large number of studies have been reported
on the use of RSM modelling for analysis and optimisation
of different processes used in water and wastewater treat-
ment. Some of these are discussed here.
Coagulation–flocculation
Coagulation is a most common process used in water and
wastewater treatment for destabilisation of the colloidal par-
ticles. Usually iron or aluminium salts are added to form
hydroxide precipitates which entrap the colloidal particles.
Overdose of coagulant can result in reduction in particle
removal efficiency and determining optimum dose is impor-
tant. Since the process is influenced by a number of factors
such as coagulant dose, pH, initial turbidity and concen-
tration of co-coagulants, RSM can be advantageously used
for finding the optimum operating conditions. Several studies
have been reported in the literature. Zainal-Abideen et al.
() performed a comparative study between the traditional
one-factor-at-a-time approach and RSM to determine the opti-
mum operating conditions using the jar test. Initial pH, alum
dose and polymer dose were the factors considered, while
final turbidity and pH, and residual aluminium were the
responses studied. A central composite design of 18 runs
including four replicates at the centre point was used in the
RSM. The optimum conditions obtained from the traditional
jar test were 12 mg/L alum dose with 0.02 mg/L polymer
dose and pH 7.6, which gave turbidity 0 NTU, settled pH
6.8 and residual aluminium 0.12 mg/L. The optimum con-
ditions with RSM were obtained by superimposing the
contour plots of the responses, and these conditions were
7 mg/L alum dose with a polymer dose of 0.004 mg/L and
pH 6.9, which produced a final turbidity of 0.64 NTU, settling
pH 6.74 and residual aluminium 0.13 mg/L. The RSM results
were verified by further tests. The study showed that the RSM
approach resulted in lower alum and polymer dosages than
the traditional approach, still producing comparable and
acceptable quality of coagulated water in terms of pH, turbid-
ity and residual aluminium.
Performances of alum and poly-aluminium chloride
were compared by using RSM (Trinh & Kang ). A
CCD with coagulant dose and initial pH as factors, and
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Water Science & Technology | 69.3 | 2014
turbidity and dissolved organic carbon (DOC) removals as
responses was used. By superimposing the contours of the
responses, optimum removals were obtained. While poly-
aluminium chloride gave turbidity and dissolved organic
carbon removals of 91.4% and 31.2% respectively, with a
dose of 0.11 mmol/L, alum produced turbidity and dissolved
organic carbon removals of 86.8% and 34.5% with a dose of
0.15 mmol/L. The authors concluded that poly-aluminium
chloride gave better performance in comparison to alum.
In a similar study, Ghafari et al. () used RSM to com-
pare performance of alum and poly-aluminium chloride
for coagulation of landfill leachate. The factors considered
were coagulant dose and pH, while the chemical oxygen
demand (COD), turbidity, colour and total suspended
solids (TSS) removals were considered as the responses.
COD removal was higher with alum, while turbdity,
colour and TSS removals were more efficient with PACl.
Liu et al. () compared the performance of different
iron-based coagulants, poly-ferric sulfate (PFS), ferric chlor-
ide and ferric sulfate for treatment of landfill leachate using
RSM, and the results showed that PFS gave better perform-
ance compared with traditional iron-based coagulants.
Other recent studies that utilised RSM in the coagulation–
flocculation process are summarised in Table 2.
Adsorption and biosorption
Adsorption and biosorption processes are used in water and
wastewater treatment, especially for removing heavy metals
and toxic organics from water. Adsorption is the process by
which the ions or molecules in a solution are condensed and
concentrated on a suitable interface. The factors playing an
important role in the adsorption process are the pH, ionic
strength, nature of the adsorbing surface, and adsorbent/
adsorbate ratio (Metcalf & Eddy ; Sawyer et al. ).
RSM has been applied to optimise operational parameters
during adsorption and biosorption, and some of these
reported studies are reviewed here.
Tripathi et al. () used RSM with Box–Behnken
Design to investigate the removal of methyl orange dye
using activated carbon as adsorbent. The factors considered
for the study were adsorbent dose (5–20 mg/L), contact time
W
(2–6 h), temperature (25–55 C) and pH (2–8). The maxi-
mum removal of 99.11% was obtained with the optimal
conditions of adsorbent dose ¼ 15.7 mg/l, contact time ¼
4 h, temperature ¼ 40 C and pH ¼ 2. Chatterjee et al.
W
() studied methylene blue removal using Parthenium
hysterophorus, a harmful weed as a low cost adsorbent.
RSM was used to statistically optimise the process variables
 470 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes Water Science & Technology | 69.3 | 2014

Table 2 | Summary of some applications of RSM in the coagulation–flocculation process

RSM Response(s)
Application Designa Independent variables studied Salient results Reference

Arsenic removal from drinking BBD Initial arsenate Arsenate 100% removal was obtained for Baskan &
water with coagulation concentration, alum removal alum dose 42–56 mg/L with Pala ()
dose and pH initial arsenate concentration of
500–1,000 μg/l at pH 7.
Coagulation using ferric chloride CCD Initial pH, coagulant Dye Dye removal of 96.53% was Moghaddam
sludge (FCS) for Acid Red 119 dosage and initial removal observed at optimum conditions et al. ()
(AR119) dye removal dye concentration of initial pH 3.5, FCS dosage
236.68 mg dried FCS/L at
65.91 mg/L initial dye
concentration.
Acid Red 119 dye removal from CCD PACl/PACl sludge Dye 95.25% and 94.1% dye removal Moghaddam
simulated wastewater using Al (PACS) dose, pH removal efficiency was observed for PACl et al. ()
based waterworks sludge and and dye and PACS respectively at
polyaluminium chloride (PACl) concentration different optimum conditions.
as coagulants PACS can offer some
advantages as a low-cost
material.
C.I. Acid Black 210 dye removal CCD Temperature, Dye 97.78% dye removal was obtained Khayet et al.
W
by aluminium sulfate aluminium sulfate removal at temperature 40 C, aluminium (b)
dose and initial pH sulfate dose of 0.82 g/L and
initial pH 5.61.
Papermaking-reconstituted CCD PACl dosage, cationic COD and 67.8% COD and 77.7% colour Wang et al. (in
tobacco slice wastewater polyacrylamide colour removals were obtained for press)
treatment (CPAM) dosage and removal PACl dose of 715 mg/L, CPAM
pH dose of 4.8 mg/L and pH 6.6.
a
BBD ¼ Box–Behnken design; CCD ¼ Central composite design.

for preparation of the adsorbent and for removal and recov-
ery of the dye. The factors considered for carbonising
conditions were weight ratio of activating agent to Parthe-
W
nium (1.0–1.5), temperature (450–550 C) and time of
carbonisation (1–2 h). The optimum conditions obtained
for the response decolourising power were weight ratio
W
1.05:1, carbonised at 550 C for 1 h. The prepared sample
was used for further study for dye removal. The factors con-
sidered for dye removal were initial concentration of dye
(25–50 mg/L), weight of adsorbent (0.2–0.5 mg/L), pH (5–
W
9) and temperature (30–40 C). A maximum removal of
99.9% was achieved with an initial dye concentration of
25 mg/L, adsorbent weight 0.5 g, pH 7 and temperature
W
35 C. For dye recovery, amount of spent adsorbent (0.2–
0.5 g), pH (5–9) and contact time (1–3 h) were the indepen-
dent variables. It was observed from the model that the
recovery rate increased with decrease in pH while it
increased with increase in contact time.
Sarkar & Majumdar () used RSM to optimise bio-
sorption of heavy metals viz. Cu(II), Ni(II) and Zn(II) on
surfactant modified chitosan bead. Half factorial design of
five factors (251) was conducted to identify the important
variables. After screening experiments, the three important
variables, pH, metal concentration and adsorbent dosage
were selected. The adsorption increased with the increase
in the dose of adsorbent due to greater availability of the
adsorbent surface. The optimum conditions for Cu(II)
adsorption were found at pH 5.5, adsorbent dosage 0.5 g/L
and initial concentration 30 mg/L through RSM with cen-
tral composite design. More applications of RSM in the
adsorption/biosorption process are summarised in Table 3.
Advanced oxidation process
Advanced oxidation involves the use of hydroxyl radicals as
strong oxidant to oxidise complex organic matter into sim-
pler end products. The hydroxyl radicals are produced by
strong oxidising agents such as ozone, hydrogen peroxide,
hypochlorite, etc. in the presence of ultraviolet rays, ultra-
sonics, photocatalysts, etc. The hydroxyl radicals react
with the dissolved contaminants, instigating a chain of oxi-
dation reactions until the contaminants are completely

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 471 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes Water Science & Technology | 69.3 | 2014

Table 3 | Summary of some applications of RSM in the adsorption/biosorption process

RSM Response(s)
Application Designa Independent variables studied Salient results Reference

Adsorption of Astrazon Red BBD Initial dye concentration Amount of dye 112 mg/g adsorption of Astrazon Santos &
(Basic Red 46) and Sirius (Cin), initial solution adsorbed Red 46 at Cin ¼ 175 mg/L, Boaventura
pHin ¼ 8.0 and T ¼ 40 C while
W
Blue (Direct Blue 85) by pH (pHin) and ()
sepiolite temperature (T) 249 mg/g adsorption of Sirius
Blue at Cin ¼ 150 mg/L,
pHin ¼ 3.5, T ¼ 30 C.
W

Bioaccumulation efficiency of CCD Initial sucrose and RTBG Growth rate of RTBG dye inhibited the growth Gönena &
Candida utilis for Remazol dye concentrations C. utilis and of yeast. Maximum RTBG Aksu ()
Turquoise Blue-G (RTBG) RTBG dye bioaccumulation of 82% by
dye removal C. utilis at 15 g/L sucrose and
50 mg/L dye concentration.
Biosorption of Cd(II) and Ni CCD Initial solution pH, initial Removal The optimum removal efficiency Fereidouni
(II) from aqueous solution Ni(II) concentration, efficiency of of 52.7% and 50.1% for Cd(II) et al. ()
onto Saccharomyces initial Cd(II) Cd(II) and and Ni(II) at initial
cerevisiae and Ralstonia concentration, and Ni(II) concentration of 28 and
eutropha biomass dosage 37 mg/L, respectively with
initial solution pH 5.0 and
2.32 g/L biomass dosage.
Biosorption of copper(II) CCD Initial pH, temperature, Copper (II) Maximum monolayer coverage Özer et al.
ions on Enteromorpha initial Cu (II) biosorption capacity of E. prolifera for ()
prolifera concentration and copper(II) ions was found to
W
biosorbent be 57.14 mg/g at 25 C, initial
concentration pH 4.0, biosorbent
concentration 1.2 g/L and
initial copper(II)
concentration 200 mg/L.
Adsorption capacity of Cu2 CCD Adsorbent concentration, Cu2þ adsorption Maximum uptake of 5.6 mg/g of Kalavathy
onto H3PO4 activated adsorbate copper ions with optimum et al. ()
carbon using rubber wood concentration, pH, conditions of initial
sawdust (RSAC) time and temperature concentration 35 mg/L,
W
temperature 26 C, carbon
loading 0.45 g/100 mL,
adsorption time 208 min and
6.5 pH.
Reactive dye biosorption by BBD pH, temperature and Dye removal 94% dye removal attained at pH Sharma et al.
W
waste biomass of Nostoc initial dye 2.0, temperature 35 C and ()
linckia concentration initial dye concentration
100 mg/L.
Optimisation of Orange G BBD Agitation time, initial dye Adsorption of Maximum 17.6 mg/L adsorption Arulkumar
dye adsorption by activated concentration and Orange G dye of Orange G dye obtained et al. ()
carbon of Thespesia adsorbent dosage with 0.54 g of activated carbon
populnea pods with an agitation time of
4.03 h.
Adsorption of crystal violet CCD Temperature, pH of Crystal violet Maximum dye adsorption of Singh et al.
dye from water by solution, dye removal 113.31 mg/g at optimum ()
magnetic nanocomposite concentration and conditions of dye
adsorbent dose concentration 240 mg/l,
W
temperature 50 C; pH 8.50,
dose 1 g/L.

(continued)

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 472 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes Water Science & Technology | 69.3 | 2014

Table 3 | continued

RSM Response(s)
Application Designa Independent variables studied Salient results Reference

Arsenic(III) adsorption on CCD Gas velocity, liquid Arsenic (III) 92.5464%. As (III) removal Dora et al.
cashew nut shale from velocity, initial static removal achieved at gas velocity of ()
aqueous solutions by using bed height and average 12.5 m/s, liquid velocity
gas–liquid–solid fluidised particle size 0.04 m/s, initial static bed
bed height 0.1 m and average
particle size 1.27 mm.
Adsorption of Cu(II) on BBD pH, Cu(II) concentration Cu(II) 62.73 mg/g of Cu(II) was Hu et al.
sulfonated magnetic and temperature adsorption adsorbed on SMGO at pH ()
graphene oxide composite 4.68, Cu(II) concentrations
(SMGO) from aqueous 3.71 mg/L, and temperature
W
solution 50 C.
Biosorption of Reactive CCD pH, dye concentration Adsorption of Maximum sorption capacity of Asgher et al.
Anthraquinone dyes by and biosorbent dose reactive blue Citrus sinensis biosorbent for ()
Citrus sinensis waste 19 and reactive blue 19 was at pH 1.5
biomass reactive blue and 0.50 g biosorbent dose
49 while for Reactive Blue 49
maximum sorption was at pH
2 and 0.05 g amount of
biosorbent.
a
BBD ¼ Box–Behnken design; CCD ¼ Central composite design.

mineralised. The hydroxyl group has a non-selective mode
of attack and can work at normal temperature and pressure.
(Metcalf & Eddy ). RSM has been employed by different
authors to optimise the process (especially for chemical
dosing) and a few of them are reviewed in this section and
other studies are summarised in Table 4.
Ay et al. () investigated advanced oxidation of direct
red 28 dye by photo–Fenton treatment using RSM. Box–Behn-
ken design was used for the experimental design. Influence of
dyestuff concentration, peroxide dose and Fe(II) dose on
colour and total organic carbon (TOC) removals were ana-
lysed. RSM models revealed that colour removal reduced
with dyestuff concentration while it increased with H2O2
and Fe(II) doses. TOC removal increased with dyestuff,
H2O2 and Fe(II) doses. At the highest initial dyestuff concen-
tration of 250 mg/L, the optimal peroxide/Fe(II) ratio was
predicted to be 715/71 mg/L for 100% colour removal,
while this ratio was 1,550/96.5 mg/L for 97.5% TOC removal.
Mohajeri et al. () investigated removal of recalci-
trant organics from semi-aerobic landfill leachate by
electro-Fenton process using RSM. A central composite
design was applied to design the experimental runs with
H2O2/Fe2þ molar ratio, current density, pH and reaction
time as input variables and COD and colour removals as
responses. To simplify the experimental design, other vari-
ables, temperature, stirring rate and distance between
electrodes were kept constant. The optimum conditions
derived were H2O2/Fe2þ molar ratio 1, current density
40 mA/cm2, pH 3 and reaction time 43 min, which pro-
duced 94.16% COD removal and 95.83% colour removal.
These values were in good agreement with the values
obtained in the verification experiments.
Electrochemical treatment
Recently, there has been an increased interest in electroche-
mical techniques such as electro-oxidation, electro-
coagulation and electro-flotation as an alternate wastewater
treatment method due to the non-biodegradable nature of
some industrial wastewaters. The major influencing factors
in the electrochemical treatment process are electrode
material, input current, pH, conductivity, electrolyte con-
centration and initial concentration of the pollutants (Sirés
& Brillas ). Several authors have used RSM to study
the influence of these factors on different electrochemical
processes. Some of the studies are discussed here. A sum-
mary of other recent studies are presented in Table 5.
Soloman et al. () investigated improvement in bio-
degradability of pulp and paper industry wastewater by
pre-treatment with the electrochemical process. RSM was
applied to optimise the operating parameters viz. current
density, electrolysis time and initial pH. Box–Behnken
design was used to derive the relationship between the
input variables and the response. The amount of anode

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 473 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes Water Science & Technology | 69.3 | 2014

Table 4 | Summary of some applications of RSM in advanced oxidation processes

RSM
Application Design Independent variables Response(s) studied Salient results Reference

2þ
Fenton process for BBD Fe dosage, H2O2 Capillary suction time (CST) Maximum CST reduction of 48 Tony
dewatering of dosage and pH reduction efficiency ±3% was obtained with et al.
aluminium based water optimal values of Fe2þ, H2O2, ()
treatment sludge and pH as 21 mg/g DS (dry
solids), 105 mg/g DS and 6,
respectively.
Fenton process for the CCD pH, H2O2/Fe(II) COD removal efficiency For pH fixed at 2, 2.5, 3, 3.5, Zhang
treatment of landfill mole ratio, Fe(II) and 4, the optimal H2O2/Fe et al.
leachate dosage (II) mole ratio were 4.7, 4.4, ()
4.0, 3.7, and 3.4 respectively.
Fenton process for BBD Initial pH, H2O2 Overall COD removal Optimum conditions at initial Wu et al.
treatment of landfill and Fe(II) efficiency, COD removal due pH 3.64, Fe2þ 100 mmol/L ()
leachate dosages to oxidation, coagulation, and H2O2 240 mmol/L.
mineralisation, HS removal,
sludge volume ratio
Fenton’s pre-treatment to CCD pH, H2O2 and iron Cyanide and phenol removals 99.002% and 100% cyanide and Kumar &
effectively remove dosages phenol removals were Pal
cyanide and phenol obtained at pH 6.09, H2O2 ()
5.45 g/L and ferrous sulfate
1.91 g/L.
Photo-Fenton process BBD Initial pH, initial ACB removal efficiency 99.6% ACB removal efficiency Xu et al.
using hydroxy-iron– dye and H2O2 was obtained at dye ()
aluminum pillared concentrations concentration of 143.7 mg/L,
bentonite for pH of 4.2 and H2O2
azocarmine B (ACB) concentration 17.7 mmol/L.
removal

dissolved, COD removal, colour removal, biodegradability
index, weight of sludge formed and the final pH were the
responses studied. The second order polynomial model gen-
erated showed that all the factors had considerable
influence on BI while the interaction terms had the least
influence. COD removal increased with increase in treat-
ment duration and current density at neutral pH. The
optimal conditions for maximum BI were: current density
112.9 A/m2, time 6.9 min and pH 7.3.
Optimisation of electrochemical treatment of textile dye
wastewater containing Levafix Blue CA, Levafix Red CA
and Levafix Yellow CA reactive dyes using RSM was inves-
tigated by Körbahti (). The input variables included
initial dye concentration (400–2,000 mg/L), current density
(1–11 mA/cm2), electrolyte (NaCl) concentration (0–4 g/L)
W
and electrolysis time (0–40 min) at 28 C, while COD,
colour and turbidity removals were the responses. The opti-
mised conditions obtained were 6.7, 5.9 and 5.4 mA/cm2 for
current density and 3.1, 2.5 and 2.8 g/L for NaCl concen-
tration for Levafix Blue CA, Levafix Red CA and Levafix
Yellow CA reactive dyes, respectively.
Other applications of RSM in water and wastewater
treatment
Recently, Moon et al. () used RSM for studying sulfate
removal by a mixed anaerobic mesophilic culture fed glu-
cose, linoleic acid and sulfate under several pH conditions
using a three factor three level BBD. The linoleic acid con-
centration, initial pH and the COD/SO2 4 ratio were the
three experimental factors studied. Increasing the COD/
SO24 ratio increased the quantity of sulfate removed. The
COD/SO2 4 ratio showed the largest effect on reducing the
sulfate level. Significant interactions between the three
experimental factors were confirmed by the surface plots,
interaction plot and ANOVA. A minimum residual sulfate
concentration of 36.2 mg/L was recorded at 1,500 mg/L
LA with a COD/SO2
4 ratio of 2.18 and a pH 6.0. Thus
the model provided a useful approach for predicting the
residual sulfate concentration in inhibited mixed anaerobic
cultures.
RSM was used for optimising the chlorination process
for landfill leachate with a CCD (Umar et al. ). The

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 474 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes Water Science & Technology | 69.3 | 2014

Table 5 | Summary of some applications of RSM in electrochemical treatment

Response(s)
Application RSM Design Independent variables studied Salient results Reference

Optimisation of CCD Waste concentration, COD removal 29.27% COD removal was Guven et al.
electrochemical treatment applied voltage, obtained after 8 hours ()
of deprotienated whey electrolyte reaction time at optimum
wastewater concentration conditions of 100% waste
concentration, 19.87 g/L
electrolyte concentration and
applied voltage 10.20 V at
W
25 C.
Optimising electrochemical Three-level Influent COD, current BOD removal, At pH 9.1 and BOD/COD ratio Bashir et al.
oxidation of landfill leachate full density and reaction COD removal, 0.04, 70% BOD removal, 68% ()
using graphite electrode factorial time BOD:COD COD removal and 84%
design ratio, colour colour removal obtained at
and pH optimum conditions of
79.9 mA/cm2 current density,
1,414 mg/L influent COD
concentration, and 4 h
reaction time.
RSM optimisation of CCD Current density, initial COD and COD and colour reduction of Kumar et al.
treatment of bio-digester pH, inter-electrode colour 50.5% and 95.2%, ()
effluent by distance and reduction respectively obtained at
electrocoagulation using electrolysis time optimum conditions of
iron electrodes current density ¼ 44.65 A/m2,
initial pH 8, inter-electrode
distance ¼ 2 cm and
electrolysis time ¼ 120 min.
Optimising organics removal CCD Current density, COD removal Optimum condition for current Kushwaha
from dairy wastewater by dosage of sodium density, sodium chloride et al.
electrochemical treatment chloride dosage, dosage, electrolysis time and ()
electrolysis time and pH were found of 270 A/m2,
pH 0 mg/L, 50 min, and 7.0,
respectively which gave
approximately 70% COD
removal.
RSM optimisation for the CCD Initial pH, current COD removal, At optimum conditions of initial Mondal
electrochemical treatment of density, electrolysis colour pH 6.6, inter-electrode et al.
textile printing dye-bath time and inter– removal and distance 0.5 cm, electrolysis ()
effluent using aluminium electrode distance specific time 102 min and current
electrode energy density 19.51 mA/cm2 , COD
consumed removal 94%, colour
removal ¼ 99.7% and specific
energy consumed ¼
0.011 kWh/kg COD removed.

effect of chlorine dose and contact time on the inactivation
of total coliforms and E. coli was evaluated. Maximum total
coliform inactivation of 59% occurred at 1 mg/L chlorine
dose and 60 s contact time, while 100% inactivation of E.
coli was obtained at the same conditions. Reducing the
chlorine dose to 90% for the same contact time gave 90%
inactivation of E. coli. Both the responses were superim-
posed upon each other to obtain the optimal conditions
using desirability function. At the optimum conditions of
43.5 s contact time and 0.91 mg/L chlorine dose, 99% inac-
tivation of E. coli and 50% inactivation of total coliform
were predicted. Results from further experiments conducted
at these optimum conditions were in agreement with the
values predicted by the model.
RSM has also been used for modelling and optimisation
of other processes such as ultrafiltration for heavy metal

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 475 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes
removal from wastewaters (Xiarchos et al. ), desalina-
tion by reverse osmosis (Khayet et al. a), ultrasound
irradiation (Lan et al. ), photolysis (Im et al. ) and
photocatlytic treatment (Ray et al. ; Sakkas et al. ).
IMPROVING RSM
While RSM has many advantages over other optimisation
procedures, it has several shortcomings also. These are
listed in Table 6. One of the most important issues to be
dealt with while using RSM is the starting point. Often,
the initial approximation of operating conditions will be
far away from the actual optimum and then the exper-
imenter has to move to the optimum region by the method
of steepest ascent or steepest descent to provide the best
combination of factors (Abbasi & Mahlooji ).
Another shortcoming is the small experimental domain.
RSM is unable to develop models over a wide range. Hence
the experimenter should have sound knowledge of the pro-
cess being studied to select the experimental domain
Table 6 | Advantages and limitations of RSM
Advantages
Generates large amount of information from a small number of
experiments
Main effects of variables and interaction effects between the
variables on the response can be studied
Models can be built that help to predict response
Graphical illustrations help in visual interpretation of the
functional relationship between the response and the
independent variables
Determine the factor levels that provide the optimum response
Multiple responses can be analysed and the optimum conditions
considering all the responses can be determined
Since the experiments are well planned, duration of the project can
be estimated
Sensitivity of a response to the factors of interest can be analysed
Limitations
Number of experiments increases with the number of independent
variables
Poor prediction capability outside the experimental domain
Fit the data only to first or second order polynomials
The factors considered should vary continuously over the
experimental domain
The model can tell what happens at different conditions but
cannot explain the mechanism of the process
Adapted from Geiger (1997); Baş & Boyaci (2007a, b); Abbasi & Mahlooji (2012).
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Water Science & Technology | 69.3 | 2014
(Geiger ). RSM uses a second order polynomial for mod-
elling which cannot explain all systems containing curvature
(Baş & Boyaci a, b).
In order to overcome the shortcomings of RSM,
attempts have been made to combine RSM with other
optimisation procedures. Artificial neural network (ANN)
is one such technique which provides nonlinear modelling
for response surfaces. ANN analysis is generally flexible in
regards to the number and form of the experimental data.
Also, combining RSM with ANN would give a superior
accuracy in data learning and prediction over the traditional
RSM (Bezerra et al. ). ANN uses all data points to pre-
dict the response. However, the number of experiments
required by ANN technique is more compared with RSM
(Geyikci et al. ).
Integration of RSM with other modelling techniques
such as fuzzy logic (Kim & Lin ), simulation annealing
(Wang & Wu ) and genetic algorithm (Khoo & Chen
) has also been investigated. These methods have been
proven to improve the RSM to determine the near optimal
values. Although this approach has been applied in several
other fields, few studies have been reported on their appli-
cation in analysing/optimising water and wastewater
treatment processes.
Integration of uniform design with RSM was attempted
by Wang et al. () for optimising the coagulation–floccula-
tion process for pulp mill wastewater treatment. With the
uniform design method, the number of experiments
needed is controlled only by the level of factors and not by
the number of factors. This method can also be used when
the levels of factors are different. Thus the integrated
approach could optimise the processes using fewer exper-
iments and would be attractive for situations where
running experiments are costly (Wang et al. ).
CONCLUDING REMARKS
RSM is a highly efficient procedure as it not only finds the
optimum operating conditions to maximise the performance
of a system but also generates a response surface model that
predicts a response based on a combination of factor levels.
Further, it gives the relative magnitude and effect of different
factors on the response and their interactions. This has led
to their use in modelling a variety of water and wastewater
treatment systems/processes, as shown in this review.
In most of the studies reported in the literature, optimis-
ation of a system/process was carried out without cost
considerations. Thus there is a need to include economic
 476 A. T. Nair et al. | RSM for modelling water and wastewater treatment processes
factors while optimising a particular system/process, and
this can be easily achieved using RSM. Further, RSM can
be used to determine a region of the factor space in which
the required operating conditions are satisfied. This is
especially relevant in water and wastewater treatment sys-
tems where different standards/specifications are to be met.
Experimenter’s knowledge of the process being studied
is crucial in achieving the correct solutions from an RSM
study. The review shows that in many studies involving
optimisation, real optimum points were not found due to
wrong selection of range of independent variables, which
results in optimum conditions being outside the experimen-
tal region. In such situations, conditions relating to the
maximum/minimum responses are wrongly reported as
optimum. This shows the importance of proper preliminary
work to decide the correct range of independent variables
during experimental design.
Although many studies are reported in the literature on
the use of RSM in water and wastewater treatment, there is
not much information on the application of this procedure
in the field. Thus, more studies relating to real-life appli-
cations of this technique are needed. Further, more
research is needed to compare and combine RSM with
other modelling techniques such as ANN and fuzzy logic
for modelling different water and wastewater treatment
processes.
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