Desalination 268 (2011) 2737

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / d e s a l

Decolourization of the reconstituted textile efuent by different process treatments:

Enzymatic catalysis, coagulation/occulation and nanoltration processes
Imen Khouni a,b, Benot Marrot b,, Philippe Moulin b, Raja Ben Amar a
a

Laboratoire Sciences de Matriaux et Environnement, Facult des sciences de Sfax, Route de Soukra Km4, 3038 Sfax, Tunisie
Universit Paul Czanne, UMR 6181, M2P2, Laboratoire de Mcanique, Modlisation et Procds Propres, Europole de l'Arbois, Bat. Laennec, Hall C, BP 80, 13545 Aix en Provence Cedex 4,
France

a r t i c l e

i n f o

Article history:
Received 16 June 2010
Received in revised form 22 September 2010
Accepted 23 September 2010
Available online 25 October 2010
Keywords:
Coagulation/occulation
Laccase catalysis
Nanoltration
Textile efuent
Reactive dye
Decolourization

a b s t r a c t
The objective of the present paper is to examine the decolourization efciency of textile efuent using
different processes: coagulation/occulation, enzymatic catalysis by commercial laccase and nanoltration. A
series of experiments are conducted on laboratory-prepared wastewaters combining chemically two reactive
dyes (Blue Bezaktiv S-GLD 150 and Black Novacron R), auxiliaries and chemicals. To optimise coagulation/
occulation and enzymatic treatment, response surface methodology is applied. Coagulation/occulation
leads to a maximum percent of colour removal of about 93% at 593 nm and 94% at 620 nm. Whereas, applied
commercial laccase catalysis reduces colour by up to 99%. Nevertheless, these two processes have not the
same behaviour on chemical oxygen demand (COD) and salinity removal since the obtained results show that
applied coagulation/occulation permits a partial removal of COD without effect on salinity. However, laccase
treatment has no effect on COD and on salinity retention. The application of the nanoltration shows excellent
performances in term of decolourization (superior to 99%). In the same time, a partial retention of COD and
salinity respectively of about 56% and 35% is obtained. Thus, nanoltration seems to be an efcient process in
colour removal of textile wastewater. The obtained permeate can be reused in the dyeing process in the textile
industry.
2010 Elsevier B.V. All rights reserved.

1. Introduction
With the increased demand for textile products, the textile
industry and its wastewaters have been increasing proportionally,
making it one of the main sources of severe pollution problems
worldwide [1]. Efuent treatment from dyeing and nishing
processes in the textile industry is one of the most signicant
environmental problems [2,3]. Since most synthetic dyes have
complex aromatic molecular structures which make them inert and
biodegradable difcult when discharged into the environment [4,5].
Through, textile processing employs a variety of chemicals
depending on the nature of the raw material and product. Some of
these chemicals are enzymes, detergents, dyes, acids, sodas and salts
[6,7]. The high consumption of reactive dyes, mainly in the cotton
industry, increases the environmental problems, due to their low
degree of exhaustion (60 - 90%) [8,9].
Dyes removal techniques such as adsorption, electrochemical
oxidation, photocatalytic oxidation, electro-Fenton oxidation appear
to face several technical and economic limitations [1012] and were

Corresponding author.
E-mail address: benoit.marrot@univ-cezanne.fr (B. Marrot).
0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.09.046

found to be inadequate [13] because most textile dyes have complex

aromatic molecular structures that resist degradation. The need for
more efcient treatment processes has attracted the attention of
environmental scientists and engineers.
For these reasons many attempts have been made to treat textile
wastewater using conventional wastewater treatment methods
[14,15]. Coagulation/occulation is widely used for wastewater
treatment, as it is efcient and simple to operate. Aluminium and
iron salts are widely used as coagulants in water and wastewater
treatment for removing a broad range of impurities from efuent,
including colloidal particles and dissolved organic substances. The
mode of action is generally explained in terms of two distinct
mechanisms: charge neutralization in negatively charged colloids by
cationic hydrolysis products and incorporation of impurities in an
amorphous hydroxide precipitate (sweep occulation). In this
process, many factors can inuence its efciency, such as the type
and dosage of coagulant/occulant [1620], pH [2124], mixing speed
and time [25,26], temperature and retention time [27,28], etc. The
optimization of these factors may signicantly increase the process
efciency. Generally, the experiments were carried out by jar test
which is usually employed to evaluate the treatment process
efciency. In the jar tests, coagulant dosage, occulant dosage and
pH were the factors that needed to be optimized [29].

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I. Khouni et al. / Desalination 268 (2011) 2737

Nomenclature
ODU
Optical Density Unit
NTU
Nephelometric Turbidity Unit
Da
Dalton
T
Temperature (C)
U.g-1
Unity per gram
U.L-1
Unity per liter
TMP
Transmembrane Pressure
i
Regression coefcient
Xi
Coded factor
RDE
Reconstituted Dyeing Efuents
ADS
Aqueous Dye Solution
CL
Commercial Laccase
CF
Coagulation/Flocculation
EC
Enzymatic Catalysis
NF
Nanoltration
CCD
Central Composite Design
RSM
Response Surface Methodology
MWCO Molecular Weight Cut Off
COD
Chemical Oxygen Demand
PAS
Polymeric Aluminium Sulphate
CC
Calcium Chloride
Al2(SO4)3 Polymeric Aluminium Sulphate
CaCl2
Calcium Chloride
NaOH
Sodium hydroxide
HCl
Hydrochloric acid
BB150
Blue Bezaktiv S-GLD 150
BNR
Black Novacron R

In the other hand, a number of biotechnological approaches have

been suggested with potential interest in reducing textile efuent
pollution source in an eco-efcient manner [30]. The enzymatic
treatment can be simpler and more efcient than the traditional
physical-chemical treatments [31]. As enzymes are highly selective
and recent researches have focussed on the development of enzyme
processes using ligninolitic enzymes (e.g. Mn peroxidase, Lignin
peroxidase and Laccase) for the treatment of textile wastewater [32].
The capability of laccases (benzenediol:oxygen oxidoreductase, EC
1.10.3.2) to act on chromophore compounds such as azo, triarylmethane, anthraquinonic and indigoid dyes suggest that they can be
applied in industrial decolourization processes [33,34]. The laccase
use in the textile industry is growing very fast, since besides to
decolourize textile efuents as commented above, laccase is used to
bleach textiles and even to synthesize dyes [35]. Laccase exhibit a
number of features that make their use advantageous, as compared to
conventional chemical or microbial catalysts such as biodegradable,
high level of catalytic efciency, high degree of specicity, easily
removed from contaminated streams, easily standardized in commercial preparations and absence of side-reactions. These characteristics provide substantial process energy savings and reduced
manufacturing costs. Nevertheless, as enzyme, laccase treatment
efciency depends on the inuence of several parameters such as 1)
Temperature: there are dened temperature ranges under which
enzymes operate and there is a specic temperature levels (optimum
temperature) in which enzymes have maximum efciency. Therefore
temperature variations affect enzymatic activity and the kinetic of the
reactions they catalyze. In addition, as proteins, enzymes can be
denatured under extreme temperatures and loses their catalytic
activity; 2) pH: the concentration of hydrogen ions in solution affects
the enzyme activity. Each enzyme has maximal efciency under an
optimum pH. Since pH is one of the factors for the denaturation of
proteins, if an enzyme is submitted to a pH level under which it is
denatured there will be no enzymatic activity; 3) Enzyme concentra-

tion: initially as substrate concentration increases, the reaction kinetic

increases; this happens because free activation centers of the enzyme
bind to free substrates. Once all activation centers of the available
enzymes become bound to their substrates new increments of the
substrate concentration will have no effect on the reaction kinetic and
4) Substrate concentration: usually a very small amount of enzyme
can consume a large amount of substrate. The rate of reaction depends
directly on the amount of enzyme present at a specic time at
unlimited substrate concentration. If two folds increase the amount of
enzyme the reaction rate is doubled. By increasing the enzyme
molecules, an increase in the number of active sites takes place. At
higher concentration of the enzyme the inhibitors will fall short. More
active sites will convert the substrate molecules into products, in the
given period of time. After a certain limiting concentration, the rate of
reaction will no longer depend upon this increase.
Finally, recently reports are available for real textile wastewater
treatment using membrane processes such as Ultraltration (UF),
Nanoltration (NF) and Reverse Osmosis (RO) [36,15]. UF is effective
as single step treatment of secondary textile wastewater. NF and RO
allow the separation of low molecular weight organic compounds and
salts. The NF permeate is usually colourless and low in total salinity
[37,38]. Membranes technologies provide an important solution in
environmental elds such as pollution reduction and water reuse,
recycling valuable components from the waste streams [39,40].
Nevertheless, the application of membrane processes has some
drawbacks like concentration polarization and fouling that result in
ux decline with time [41]. However, ux can be improved by
adjusting the ltration conditions such as pH, temperature, pressure
and velocity [42].
In the present investigation, maximum dye decolourization ability
of CF treatment and CL catalysis was studied adopting a full range of
response surface methodology (RSM) using central composite design
(CCD) model to analyze the affectivity of the two systems under
different conditions. Then, obtained CF and CL decolourization
efciencies are compared to those achieved under NF process.
2. Materials and methods
2.1. Dyes and reconstituted textile efuents
Two reactive dyes were used to prepare simulated textile efuents.
They were reactive Black Novacron R (BNR) and Blue Bezaktiv S-GLD
150 (BB150) dyes provided by SARTEX (textile manufacturing unit in
Ksar Helal (Tunisia)) and which were purchased from BEZEMA AG
and from HUNTSMAN Textile Effects CH-4057 Ble respectively.
Reactive BB150 and BNR textile dyes were chosen since they are
widely used to colour cellulose bres. The characteristics of the two
reactive dyes chosen are given in Table 1.
For the decolourization study and in order to imitate the textile
wastewater, a synthetic (reconstituted) efuent was prepared based
on real process information's of dyeing stages of cotton bre (Jeans)
according to the SARTEX. Two synthetic dyeing efuents were used:
Table 1
Properties of the reactive BB150 and BNR dyes at a concentration of 1 g/L.
Parameters

Unit

BB 150

BN R

max
Absorbance at max
Dry matter (DM)
Mineral matter (MM)
Volatile matter (VM)
BOD5
COD
Turbidity
Chemical group
Chromophore

nm
ODU
%
%
%
mg O2/ g
mg O2/ g
NTU
-

620
15.94
91.93
70
30
300
840
b1
Reactive
Not available

593 - 400
26.30 15.37
96.57
68.66
31.34
272
850
b1
Reactive
Azoic

I. Khouni et al. / Desalination 268 (2011) 2737

Table 2
Composition of the two synthetic textile efuents used : RDE and ADS.
Components

Reactive dye (BB150; BNR)

Sodium hydroxide (NaOH)
Sodium carbonate (Na2CO3)
Cibacel DBC (Detergent)
Beavin BPA
Sodium chlorate (NaCl)

Unit

Concentration

-1

mg.L
mg.L-1
mg.L-1
mg.L-1
mg.L-1
g.L-1

RDE

ADS

40
80
200
40
40
4

40
0
0
0
0
0

aqueous dye solutions (ADS) with 40 mg.L-1 of the appropriate dye

(BB150 or BNR) and reconstituted dye efuents (RDE) using the same
dye concentration and auxiliary components (Sodium hydroxide,
Sodium carbonate, Cibacel DBC, Beavin BPA and Sodium chlorate) as is
described in Table 2. Prior to use, the synthetic dye solutions were
hydrolysed at 60 C for 2 hours. They were then cooled at room
temperature and the pH was adjusted with HCl or with NaOH.
2.2. Enzyme
Commercial laccase formulation (DeniLite IIS; 120 U/g) produced from genetically modied Aspergillus oryzae was purchased
from Novozymes. This laccase formulation was usually used for indigo
dye decolourization in jean nishing operations and includes a buffer
and an enzyme mediator.
2.3. Chemicals
All of the chemicals used were of analytical reagent grade. Calcium
Chloride (CaCl2) and Polymeric Aluminium Sulphate Al2(SO4)3 were
utilized during the coagulation/occulation (CF) experiments and
applied to test their capability for textile efuent coagulation on a
laboratory scale. Calcium Chloride (CC) and Polymeric Aluminium
Sulphate (PAS) were prepared in solutions at 100 g.L-1 of concentration. Two occulants were tested during these experiments: sodium
poly-metachrelate and CHT-Floculant CV (of industrial grade
occulants).
Sodium hydroxide (NaOH) and Hydrochloric acid (HCl) were used
in order to adjust the pH of the synthetic dyeing solutions used. Other
chemicals (Table 2) are added to obtain the same composition of the
dyeing bath used by SARTEX and were kindly provided by this textile
manufacturing unit.
2.4. Cross-ow ltration
A NF pilot plant was employed for decolourization of RDE and of
ADS (Fig. 1). Cross-ow NF process decolourization was conducted
with NF DK 2540F-standard membrane characterised by a total
surface area of 2.5 m2, a length of 1.05 m, a cut-off of 200 Da and a
permeability of 8 L.h-1.m2.bar-1. All experiments were conducted with
a xed dye concentration of 40 mg.L-1 and at an efuent ow rate of
80 L.h-1.m-2. During the NF operation, permeate and retentate were
sent back to the feed tank to ensure a constant concentration of the
feed solution. Previously, membrane permeability was determined
using pure distilled water. Afterwards, it was exposed to RDE and to
ADS at a temperature equal to 25 C. After the measurements, the
membrane was rinsed with distilled water and the fouled membrane
permeability was measured with distilled water.

29

Flocculant CV were tested on their decolourization capability at pH range

between 5 and 9. Each coagulant was added separately and rapidly mixed
at 180 rpm during 3 min. Then occulant was added and the speed was
reduced to 30 rpm for 15 min. Afterwards, we let particles settle down for
about 15 min [43]. After settling, samples were taken for analysis.
Enzymatic catalysis with CL was conducted in 250 mL erlenmeyers
asks under stirring during 1 day and pH values of synthetics dye
solutions were established by buffer preparation: 50 mM of citrate/disodium hydrogen phosphate for pH 3 and 50 mM of di-sodium
hydrogen phosphate for pH 5 and pH 7 [44].
In the second step, optimization of CF treatment and of CL catalysis
was aimed through batch runs using RSM approach.
Table 3 indicates that during these assays, three parameters have
been investigated for each treatment. For EC, only temperature, pH
and enzyme concentration have been selected since we have treated a
reconstituted dying efuent with a xed substrate concentration (dye
concentration of 40 mg/L). For CF treatment, in the jar tests, coagulant
concentration, occulant dosage and pH were the factors that have
been chosen to be optimized since we have chosen to work in real
conditions of SARTEX Company in terms of ambient temperature,
mixing degree and reaction time. Optimal conditions were determined for the best colour removal. The runs were designed in
accordance with the central composite design (CCD).
2.6. Optimization of CF and EC decolourization processes
Since the conventional method of optimization, one factor at a
time approach is laborious, time consuming and incomplete,
response surface methodology (RSM) using central composite design
(CCD) was applied to model the decolourization process. This
approach (RSM) is a collection of mathematical and statistical
techniques for empirical model building [45]. By careful design of
experiments, the objective is to optimize a response (output variable)
which is inuenced by several independent variables (input variables).
An experiment is a series of tests, called runs, in which changes are
made in the input variables (parameters) in order to identify the
reasons for changes in the output response.
In the present investigation, the RSM study was conducted to
determine the relative contributions of three predictor variables
(temperature, pH and laccase concentration) for textile dye catalysis
using CL and (coagulant concentration, pH and occulant concentration) for textile dye decolourization under CF treatment. For this a
three-level BoxBehnken full factorial design was employed [45] to
investigate and validate process parameters affecting the textile dye
decolourization under CF and CL treatments. A total of 29 experiments
were performed for each optimization.
The CCD model based on three factors was used as experimental
design model. The factor levels were coded as 1 (low), 0 (central point)
and +1 (high) [46]. Table 3 shows experimental parameters and the Box
Behnken design levels used respectively for CF process and for CL catalysis.
Linear and quadratic models are so establish, their accuracies are
determined by comparing lacks of t of model predictions to experimental
points with experimental error estimated from replicates at the central
point. Moreover, to study the effects of the various parameters, statistical
analysis were done using NemrodW version 2000-D [47]. To obtain the
regression equations, linear and second-order polynomials were xed to
the experimental data. The sequential F-test, and other adequacy
measures were used in selecting the nest model [48].
Colour removal percentage (Y) was taken as the response of the
design experiments. Experimental data obtained from the CCD model
experiments for either CF or CL treatments can be stated by Eq. (1):

2.5. Coagulation/occulation treatment and enzymatic catalysis

In the rst step, Jar-test experiments were conducted on synthetic
dye solutions in different graduated glass beakers. Two coagulants: CC
and PAS, and two occulants: sodium poly-metachrelate and CHT-

k1

Y = 0 + i xi + ij xi xj + ij xi +
i=1

i=1 j=2

i=1

30

I. Khouni et al. / Desalination 268 (2011) 2737

Fig. 1. Nanoltration pilot plant.

Where 0 is the constant, i is the linear effect of the input factor

Xi, ij is the linear by linear interaction effect between the input
factors Xi and Xj, ij is the quadratic effect of input factor Xi and is the
error [49].
The results of the experimental design, regression and graphical
analysis of the data obtained were analyzed and interpreted using
NemrodW version 2000-D statistical software [47]. The sequential Ftest, and other adequacy measures were used in selecting the nest
model [48].

2.7.2. COD determination

COD was estimated by open reux method. The sample was
reuxed in an acidic medium with a known excess of potassium
dichromate and the remaining dichromate was titrated with ferrous
ammonium sulphate. The conductivity was determined by Consort K
220 conductivity meter. Turbidity was measured using a turbidity
meter (Hach chemical co, Loveland, co) in accordance with standard
method 2130B; a calibration standard is needed.
3. Results and discussion

2.7. Analytical measurements

3.1. Coagulation/occulation treatment
Colour, COD, and conductivity were determined according to the
standard methods suggested by American Public Health Association
[50]. For colour and COD analysis, samples were centrifuged at
10000 rpm for 15 min and analyzed for residual dye concentration in
term of colour intensity and for COD.
2.7.1. Colour determination
Colour measurement was determined with standard dilution
multiple method [51] and by comparing absorbance to a calibration
curve [44]. Dye decolourization was determined by monitoring the
decrease in the absorbance peak at the maximum wavelength for each
dye: for BNR dye, maximum wavelengths were at 593 nm and at
400 nm whereas for BB150 dye only one pick was observed with
maximum wavelength at 620 nm. UV-visible spectrophotometer
(Shimadzu UV 1650 PC) was used in all experiments.
Table 3
Independent variables and levels used for the optimization study of CL catalysis and CF
treatment.
Coded
factors

Factors

Enzyme catalysis using commercial laccase

X1
Temperature (C)
X2
pH
X3
Enzyme (U.L-1)
Coagulation/Flocculation treatment
X1
Coagulant concentration (g.L-1)
X2
pH
X3
Flocculant concentration (g.L-1)

Coded level
-1

+1

25
3
80

35
5
160

45
7
240

1.0
5
2

1.5
7
3

2.0
9
4

The experimental results by application of Jar-test indicated that

the use of PAS as coagulant combined with the CHT-Flocculant CV
appeared to be the appropriate choice with the highest colour
removal efciency and the least coagulants and occulants consumption. Subsequently, RDE and ADS were subjected to CF treatment
using PAS as coagulant combined with the CHT-Flocculant CV.
Therefore, the CCD has been applied to optimize three most important
operating variables: pH, coagulant and occulant concentrations.
Table 4 shows the coded experiments conducted as per experimental
design along with the response values. Maximum rates of colour
removal are registered at the Table 5.
The obtained results show that CF treatment gave high colour
removal rates as about 94% for both reconstituted and aqueous BB150
solutions. Else, for the reactive BNR dye, CF treatment gave 93% of
colour removal for both reconstituted and aqueous BNR solutions at
the wavelength of 593 nm (85% and 88% respectively for aqueous and
reconstituted BNR solutions at the wavelength of 400 nm). So, CF
treatment of the two reactive dyes (BB150 and BNR at the wavelength
of 593 nm) have the same colour retention yields regardless of the
type of solution treated (salts and auxiliary (NaOH, Na2CO3, Cibacel,
Beavin and NaCl) have no effect on CF decolourization). Whereas, for
BNR, presence of salts and auxiliary in RDE has increases slightly the
colour removal at the wavelength of 400 nm.
Further RSM steps, the statistical analysis of CCD experimental
results, response surface modelling and optimization of process
variables were carried out using NemrodW software. For RDE, the
statistical analysis employed Fisher's F test and Student's t test were
registered at Tables 6 and 7 (data were not shown for ADS). In general,

I. Khouni et al. / Desalination 268 (2011) 2737

the larger magnitude of t and the smaller value of p, more signicant

is the corresponding coefcient term [52].
According to the sequential model sum of squares, the models
were selected based on the highest order polynomials where the
additional terms were signicant. The experimental results were
evaluated and the different predicted responses (Y) for percent colour
removal of samples treated were obtained in Eqs. (2) to (7):
2

Y620 = 94 + 1:125X1 + 8X2 + 0:625X3 7:875X2 X1 X2 X2 X3

Table 5
Maximum percentages of colour removal obtained experimentally under CF treatment.
Dye

BB 150

Wavelength
Initial colourization
Final colourization
Colour removal
Run N

Y620 = 93 + X1 + 7:875X2 7X2

31

BNR

Unit

ADS

RDE

ADS

RDE

nm
ODU
ODU
%

620
0.559
0.033
94
7, 8, 23, 24

620
0.557
0.033
94
7, 8, 11,
12, 15,
16, 19,
20, 23,
24, 25,
26, 27,
28, 29

593 - 400
0.542 - 0.309
0.043 0.046
93-85
23

593 - 400
0.541 - 0.3
0.037- 0.036
93-88
5, 6, 7, 8, 19,
20, 23, 24, 25,
26, 27, 28, 29

3
2

Y593 = 93 + 11:5X2 + 0:392X3 1:107X1 10:392X2 1:107:X3

2

Y593 = 921:875X1 + 9:688X2 + 5:313X3 3:312X1 5:188X2 9:937X3

+ 8:5X1 X2 + 1:25X1 X3 0:625X2 X3

interaction between the two factors and quadratic effect, respectively.

The models established for ADS and RDE were different for the two
reactive dyes treated. This result can be explained by the presence of
auxiliary components (Sodium hydroxide, Sodium carbonate, Cibacel
DBC, Beavin BPA and Sodium chlorate) in RDE which inuence the
behaviour of coagulants and occulants used. For all models, analysis
of variance (NemrodW) for percentage of decolourization shows that
tted second order response surface model is highly signicant
(Table 7).
The R2-value of 0.990 for Eq. (2), of 0.999 for Eq. (4) and of 0.998
for Eq. (6) and the R2 of 0.990 for Eq. (3), and of 0.931 for Eq. (7) were
considered relatively high indicating that there was a good agreement
between the experimental and the predicted decolourization uptake
from this model (tables of statistical analysis of aqueous dye solutions
were not shown). The regression coefcients and the interaction
between each independent factor can be considered statistically
signicant for p-values below 0.01, with 99% of condence interval.

5
2

Y400 = 88 + 14X2 + 0:75X3 1:75X1 12:25X2 1:75:X3

2

Y400 = 855X1 + 7:5X2 11:875X1 11:875X3 + 13:75X1 X2

whereY(620) and Y(620) are colour removal of RDE and ADS of reactive
BB150 dye at 620 nm. Y(593), Y(593),Y(400) and Y(400) are colour
removal of RDE and ADS of reactive BNR dye at 593 nm and at 400 nm
respectively. X1, X2 and X3 are independent variables of coagulant
concentration, pH and occulant concentration respectively.
Positive sign indicates synergistic effect, whereas negative sign
indicates antagonistic effect. The model quality developed was
evaluated on the correlation coefcient value. Coefcients with one
factor represent the particular factor effect, while coefcients with
two factors and those with second-order terms represent the

Table 4
Experimental results of CCD designed experiments for CF treatment and for CL catalysis of RDE and ADS at 40 mg.L-1 dyes concentration.
Run
no.

Factors

% Colour removal (Y) for CF treatment

BNR dye

X1

X2

g.L-1
1
2
3
4
5
6
7
8
9
10
11
12
3
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29

10
10
20
20
10
10
20
20
10
10
20
20
10
10
20
20
15
15
15
15
15
15
15
15
15
15
15
15
15

5
5
5
5
9
9
9
9
7
7
7
7
7
7
7
7
5
5
9
9
5
5
9
9
7
7
7
7
7

BB150 dye

Run
no.

Factors

BNR dye

X3

= 593 nm

= 400 nm

= 620 nm

X1

g.L-1

RDE

ADS

RDE

ADS

RDE

ADS

3
3
3
3
3
3
3
3
2
2
2
2
4
4
4
4
2
2
2
2
4
4
4
4
3
3
3
3
3

70
70
70
70
93
93
93
93
90
90
90
90
91.57
91.57
91.57
91.57
70
70
93
93
70
70
93
93
93
93
93
93
93

92
92
60
60
90
90
92
92
70
70
75
75
80
80
90
90
60
60
85
85
70
70
93
92
92
92
92
92
92

60
60
60
60
88
88
88
88
83
83
83
83
86
86
86
86
60
60
88
88
60
60
88
88
88
88
88
88
88

85
85
40
40
70
70
80
80
65
65
60
60
60
60
60
60
60
60
70
70
60
60
85
85
85
85
85
85
85

75
75
80
80
93
93
94
94
92
92
94
94
93
93
94
94
76
76
94
94
80
80
94
94
94
94
94
94
94

77
77
80
80
92
92
94
94
90
90
92
92
92
92
93
93
78
78
93
93
75
75
94
94
93
93
93
93
93

1
2
3
4
5
6
7
8
9
10
11
12
3
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29

% Colour removal (Y) for CL catalysis

25
25
45
45
25
25
45
45
25
25
45
45
25
25
45
45
35
35
35
35
35
35
35
35
35
35
35
35
35

X2

3
3
3
3
7
7
7
7
5
5
5
5
5
5
5
5
3
3
7
7
3
3
7
7
5
5
5
5
5

BB150 dye

X3

= 593 nm

= 400 nm

U/L

RDE

ADS

RDE

ADS

= 620 nm
RDE

ADS

160
160
160
160
160
160
160
160
80
80
80
80
240
240
240
240
80
80
80
80
240
240
240
240
160
160
160
160
160

81.61
81.61
84.73
84.73
94.60
94.60
98.93
98.93
89
89
95
95
93
93
97
97
88
88
98.70
98.70
89
88
98.90
98.90
98.40
98.40
98.40
98.40
98.40

93.80
93.80
94
94
97
97
97.50
97.50
94.20
94.10
94.40
94.30
94.30
94.20
95
95
94.20
94.20
98.50
98.50
95.20
95.20
98.40
98.40
97.50
97.50
97.50
97.50
97.50

32.05
32.05
72.90
72.90
74.74
74.60
79.90
79.90
0
0
61.40
61.50
0
0
59.20
59.20
0
0
79.90
79.85
6
5.97
59.30
59.35
59.35
59.30
59.35
59.34
59.33

0
0
73.90
73.90
79
79
80.10
80.10
20
20
65
65
30
30
62
62
0
0
81.20
81.20
0
0
73.10
73
73
73
73
73
73

95.68
95.71
96
96.07
96.51
96.55
98.90
98.90
95.70
95.70
97.80
97.80
97.81
97.81
98.20
98.20
95.80
95.80
98.04
98.04
94.70
94.70
98.20
98.20
98.12
98.12
98.12
98.12
98.12

95.89
95.99
96.21
96.20
98
98
98.80
98.80
97.80
97.80
98.70
98.70
96.65
96.65
97.80
97.80
96.50
96.50
99
99
96.50
96.50
99
99
98.10
98.10
98.10
98.10
98.10

32

I. Khouni et al. / Desalination 268 (2011) 2737

Table 6
Estimated regression coefcient for CF treatment of RDE (BB150 and BNR).
R.C.

Coefcient value
BNR

F. Ination
BB150

BNR
593

(nm)

593

400

620

0
1
2
3
11
22
33
12
13
23

93
0
11.5
0.392
-1.107
-10.39
-1.107
0
0
0

88
0
14
0.75
-1.75
-12.25
-1.75
0
0
0

94
1.125
8
0.625
-0.625
-7.875
-0.125
-1
-0.25
-1

1
1
1
1.03
1.03
1.03
1
1
1

BB150
400
1
1
1
1.03
1.03
1.03
1
1
1

Standard deviation

t exp.

BNR

BNR

BB150

p value
BB150

BNR

BB150

620

593

400

620

593

400

620

593

400

620

1
1
1
1.03
1.03
1.03
1
1
1

0.161
0.090
0.090
0.090
0.137
0.137
0.137
0.127
0.127
0.127

0.308
0.172
0.172
0.172
0.261
0.261
0.261
0.243
0.243
0.243

0.218
0.122
0.122
0.122
0.185
0.185
0.185
0.172
0.172
0.172

577.36
0
127.71
4.36
-8.11
-76.10
-8.11
0
0
0

285.91
0
81.37
4.36
-6.71
-46.94
-6.71
0
0
0

431.90
9.25
65.75
5.14
-3.39
-42.68
-0.68
-5.81
-1.45
-5.81

b 0.01 ***
100
b 0.01 ***
0.0338 ***
b 0.01 ***
b 0.01 ***
b 0.01 ***
100
100
100

b0.01 ***
100
b0.01 ***
0.0338 ***
b0.01 ***
b0.01 ***
b0.01 ***
100
100
100

b 0.01 ***
b 0.01 ***
b 0.01 ***
b 0.01 ***
0.309 **
b 0.01 ***
50.6
b 0.01 ***
16.3
b 0.01 ***

R.C.: Regression Coefcient; p value: the signicance of the test; ***: extremely signicant.

These results indicate that the accuracy of the polynomial models is

well adapted.
The graphs obtained for all synthetic solutions treated show the
same behaviour with the uctuation of independent variables of
coagulant concentration, pH and occulant concentration. It must be
notied that no plot differences were observed between the two
reconstituted BNR and BB150 dyes and between RDE and ADS treated.
It follows from this that only three-dimensional response surface plots
for colour removal of RDE (for both BB150 and BNR) are represented.
For all RDE treated, the three-dimensional (3D) surface plots show the
relative effects on decolourization rates of any two variables when the
remaining (third) variable was kept constant (Figs. 2, 3 and 4). Surface
plot 2A in these gures shows the interactive effect on decolourization
rate of occulant concentration and pH by keeping coagulant
concentration constant at 1.5 g.L-1. Similarly, by keeping pH constant
at 7, surface plot 2B shows the interactive effect on colour removal of
occulant and coagulant concentrations. Finally, surface plot 2 C
shows the interactive effect for colour removal between pH and
coagulant concentration by keeping occulant concentration constant
at 3 g.L-1. The 3D surface plots shows that the best colour removal of
reconstituted BNR efuent at 593 nm and at 400 nm was obtained at
basic pH (Figs. 2 and 3). It was also observed from the plots A and C
(Figs. 2 and 3) that at pH range between 5 and 8.5, the colour removal
increases when pH increases. However at the maximum pH values,
colour removal decreases (results are obtained for all sample used).
Thereby, beyond 9 the decolourization yield falls.
On the other hand, the 3D surface plots 2B and 3B (Figs. 2 and 3)
show that variation of coagulant and occulant concentrations in the
eld test at xed pH has no effect on colour removal of reconstituted
BNR efuent. For reconstituted BB150 efuent, similar 3D surfaces
plots for percent colour removal as those as of reconstituted BNR

efuent were obtained and same interpretations were drawn (Fig. 4).
Indeed, from the 3D surface plots 4A and 4 C, the best colour removal
was obtained at basic pH below value of 9. From 4B surface plot we
observed that, at xed pH, coagulant and occulant concentrations
have no effect on colour removal.
Optimum colour removal of the reconstituted BB150 efuent
predicted from the models (95.75 %) occurs when the coagulant and
occulant concentrations were about 1.842 g.L-1 and 3.82 g.L-1
respectively at pH 8.2 (Table 8). For BNR (RDE and ADS) maximum
yields decolourization obtained at the optimum conditions described
in Table 8 were 94.21% at 593 nm and 89.57 % at 400 nm and they
were calculated from the regression equation.
Graphical response surfaces were used to identify the optimum
point. Satisfactory prediction equations were derived for colour
removal using RSM to optimize the parameters.
Obtained results demonstrated the applicability of CF method for
dye removal. In fact, under optimal values of process parameters, high
colour removal (N94%) was obtained for all dye solutions treated
containing BB150 or BNR reactive dyes.
Nevertheless, after CF treatment, the pH was decreased to a value
between 5 and 6 resulting in pH regulation to the discharge standards
(pH = 7) by adding NaOH solution. So, the major disadvantage of this
type of treatment is due to the addition of chemicals which increase
the cost of the CF process.
3.2. Laccase decolourization
The aim of this part is rstly to test the ability of a commercial
laccase (CL) formulation containing a specic mediator (DeniLite IIS)
and a pure laccase (DeniLite Base) for catalysis of reactive BB150 and
BNR dyes and, secondly, to determine the operative and the optimum

Table 7
Analysis of variance (NemrodW) for the tted quadratic polynomial models of CF treatment of RDE (effect of coagulant concentration, pH and occulant concentration).
Sources of Degree
variation
of
freedom
(DF)
(nm)
Regression 9
Residual
Total

19
28

Sum of squares (SS)

Novacron R

Mean Square (MS)

S-GLD 150

Novacron R
593

400

Ratio / F

statistics

S-GLD 150

Novacron R

620

593

S-GLD 150

620

620

593

400

620

2.87058E+
03
2.46490
2.87304E +
03

4.18921E +
03
9
4.19821E +
03

1.50481E + 3.18953E + 4.65467E + 1.67201E + 2458.5620 982.6535 705.9604

03
02
02
02
4.5
1.29732E-01 4.73684E-01 2.36842E-01
1.50931E +
03

p value: the signicance of the test; *** : extremely signicant.

R2 = 0.999 for reconstituted BNR efuent at 593 nm; (R2 = 0.851 for aqueous BNR solution at 593 nm).
R2 = 0.998 for reconstituted BNR efuent at 400 nm; (R2 = 0.931 for aqueous BNR solution at 400 nm).
R2 = 0.997 for reconstituted BB150 efuent at 620 nm; (R2 = 0.990 for aqueous BB150 solution at 620 nm).

400

S-GLD 150 Novacron R

593

400

b 0.01 *** b 0.01 *** b0.01 ***

I. Khouni et al. / Desalination 268 (2011) 2737

Fig. 2. Three-dimensional response surface plot for percent colour removal of

reconstituted BNR efuent at 593 nm using CF treatment as a function of: (A) occulant
concentration and pH, (B) occulant and coagulant concentrations, (C) coagulant
concentration and pH.

decolourization conditions of these dyes. Laccase based decolourization treatments are potentially advantageous to bioremediation
technologies since the enzyme is produced in larger amounts [53].
RSM and the CCD model were used to establish the best conditions for
the CL treatment. The optimization study of colour removal of RDE
and of ADS based on BB150 and on BNR using CL was produced similar
to the optimization study using CF treatment. Table 4 shows the coded
experiments conducted as per experimental design along with the

33

Fig. 3. Three-dimensional response surface plot for percent colour removal of

reconstituted BNR efuent at 400 nm using CF treatment as a function of: (A) occulant
concentration and pH, (B) occulant and coagulant concentrations, (C) coagulant
concentration and pH.

response values. The optimum colour removals obtained are presented in Table 9.
The optimum values predicted from the experimental models at
maximal percent colour removal (above 99%) are registered at the
Table 8. The results demonstrate that the enzyme concentration used
depends on the type of dye treated and of components added to
synthetic efuents. The results obtained are very promising and reveal
the high potential of CL to reactive dyes decolourization.

34

I. Khouni et al. / Desalination 268 (2011) 2737

Table 8
Optimum values of variable factors studied for the maximum decolourization of RDE
and ADS under CF treatment and CL catalysis.
Dyes

BB150

Samples

ADS

Enzyme catalysis using commercial laccase

(X1): Temperature (C)
38
(X2): pH
6.92
-1
(X3): Enzyme concentration (U.L )
80.19
Coagulation/occulation treatment
(X1): PAS concentration (g.L-1)
1.805
8.47
(X2): pH
(X3): CHT-Flocculant CV (g.L-1)
3.76

BNR
RDE

ADS

RDE

41.9
5.91
220.65

40.82
6.7
183.89

43
6
222

1.842
8.2
3.82

1.804
8.31
3.85

1.925
8.55
3.69

rendering the azo dye more susceptible to hydrolysis and nitrogen is

eliminated in molecular form as is described below (Eq. (8)):
8

Dye + O2 Laccasecatalysis Oxidized dye + H2 O

So, laccase can be used for treating textile dyeing wastewaters,

particularly for water recycling.
3.3. Cross ow ltration

Fig. 4. Three-dimensional response surface plot for percent colour removal of reconstituted
BB150 efuent at 620 nm using CF treatment as a function of: (A) occulant concentration
and pH, (B) occulant and coagulant concentrations, (C) coagulant concentration and pH.

The inuent ux is one of the most important parameters in the

evaluation of the performance of a nanoltration system. The colour
and COD retention are inuenced by the temperature, operation time
and transmembrane pressure.
As temperature increased from 25 to 50 C, the ux was slightly
increased with a rate of about 11% and 12% respectively for aqueous
BB150 and BNR solutions and of about 16% and 17% respectively for
reconstituted BNR and BB150 dying efuents (Fig. 5). In fact, the
variation of permeate ux with temperature is usually explained by
the variation in the viscosity of the efuent [15]. Moreover increasing
the temperature enhances the diffusivity, which results in an increase
in permeation ux. In our case, in the range of 25 to 50 C, the
temperature moderately inuences the permeate ux. In addition,
different permeate samples were collected and analysed for residual
colour. Obtained results have demonstrated that the temperature has
no inuence on the retention dye solutions and a percent colour
removal of about 99% was observed for all solutions treated (RDE and
ADS). For these reasons, in the sequel, the remaining experiments
were performed at room temperature equal to 25 C to minimize the
energetic costs of experiments.
The permeate ux variation with time for initial pure water and for
the synthetic dyeing efuents treated are presented in Fig. 6. A
decrease of permeate ux was observed for all solutions treated,
which was stabilised after 20 min of operation. For reconstituted
BB150 and BNR efuents, the presence of salts component leads to a
further decrease in ltration performances. In fact, the stabilized
permeate ux was lower than that obtained with aqueous dye
solutions (Fig. 6). During NF treatment, the colour removal remained
constant at 99% for all solutions ltered. The molecular weight cut off

Table 9
Maximum percentages of colour removal obtained experimentally under CL treatment.

In fact, according to Chivukula and Renganathan [54], the

mechanism of laccase mediated azo-dye decomposition proceeds
rst via two sequential electron abstractions. This is followed by an
attack of the nucleophile water on the resulting resonance stabilized
cation. Subsequently, breakdown of the dye molecule concomitantly
to the release of one proton and one molecule N2 takes place yielding
chinoid aromatics and transient hydroperoxides, respectively [54].
The main function of the laccase-catalysis thus consists of oxidatively

Dyes

Wavelength
Initial colourization
Final colourization
Colour removal
Run N

BB150

BNR

Unit

ADS

RDE

ADS

RDE

nm
ODU
ODU
%

620
0.559
0.006
99
19, 20,
23, 24

0.557
0.0061
98.9
7, 8

593 - 400
0.542 - 0.309
0.005 0.061
98.5 - 81.2
19, 20

593 - 400
0.540 - 0.3
0.0058 0.0603
98.93 - 79.9
7, 8

45

100

40

90

Permeate flux (L.h-1 .m-2 )

Permeate flux (L.h-1.m2)

I. Khouni et al. / Desalination 268 (2011) 2737

35
30
25
20
15
10
5

35

80
70
60
50
40
30
20
10

0
20

25

30

35

40

45

55

50

0
0

Temperature (C)
Blue S-GLD 150
dye solution

Reconstituted Blue SGLD 150 effluent

Black Novacron R
dye solution

Reconstituted Black
Novacron R effluent

10

12

14

18

16

TMP (bar)

Fig. 5. Variation of permeate ux with temperature for different synthetic efuent.

Blue Bezaktiv S-GLD 150

dye solution

Reconstituted Blue
Bezaktiv S-GLD 150 dye
effluent

Reconstituted Black
Novacron R dye effluent

Distilled water

Black Novacron R dye

solution

Fig. 7. Variation of the permeate ux with TMP for different synthetic efuents [T= 25C].

(MWCO) explains that the retention of the relative high molecular

weight dyes (such as reactive BB150 dye or BNR dye used in dyeing bath
composition and ned in textile wastewater) is always almost 100%. The
permeate ux variation have the same behaviour whatever the type of
solution treated (RDE or ADS). It seems that the performance of NF
process for retention dyes is conditioned by only the efuent.
The variation of permeate ux with operating TMP was studied
(Fig. 7). Results show that uxes increased with the increase of TMP in
the range of 8 to 12 bar. Additional experiments have demonstrated
that the TMP has also no inuence on the retention dye solutions and
a percent colour removal of about 99% was observed for all solutions
treated (RDE and ADS) at TMP values varied from 8 to 12 bars.
Different permeate samples were collected at a pressure of 10 bar and
colour was analyzed (Table 10).
The use of NF membrane allows colour removing higher than 99%
for all samples treated. These results prove that an appropriate NF
membrane cut-off gives excellent performances for the treatment of
dyeing efuents (in retaining dyes molecules). NF has proved an
efcient process to remove dyes from both RDE and ADS treated.
3.4. Comparative Study
Rates of colour removal, COD retention, conductivity depression
and turbidity of RDE and of ADS treated by CL catalysis and by CF

Table 10
Decolourization rates of RDE and ADS using tangential nanoltration.
Dyes

BB150

BNR

Samples

Unity

ADS

RDE

ADS

RDE

Wavelength
Absorbance
Coloration after NF
Colour removal
Inuent Conductivity
Conductivity after NF
Conductivity removal

(nm)
(ODU)
(ODU)
(%)
(S/cm)
(S/cm)
(%)

620
0.604
0.001
99.8
22
12
45.45

620
0.596
0.002
99.6
5450
3542
35

593 - 400
1.06 - 0.6
0.008 - 0.006
99.2 - 99
21
12
42.8

593 - 400
0.999 - 0.595
0.005 - 0.004
99.4 - 99.3
5370
3425
36.2

treatment when maximum colour removals were achieved and under

NF process are presented in Table 11. Both CL and NF are able to
decolourize the RDE and ADS with very high colour removal
percentages (N98%). CF treatment is also able to decolourize the
synthetics dyes solutions treated but with a maximum colour removal
of 94%. Moreover, CL is able to decolourize completely reconstituted
and aqueous BB150 solutions. While BB150 did not show any colour
change after CL decolourization and no additional peaks of absorbance
were observed in the entire visible spectrum (data not shown), a light
orange colour was appeared after BNR treatment by CL (Fig. 8).

80

-1

-2

Permeate flux (L.h .m )

100

Table 11
Characterization of RDE and ADS under NF process and after CF and CL treatment when
maximum colour removals were achieved.

60

Colour removal
%

40

COD
retention
%

Conductivity
removal
%

Turbidity
NTU

20
0
0

20

40

60

80

Reconstituted Blue
S-GLD 150 effluent

Reconstituted Black
Novacron R effluent

Flux (Distilled water)

Treatment

RDE

ADS

RDE

ADS

RDE

ADS

RDE

ADS

BB150

NF
CF
CL
NF

99.6
94
98.9
99.4 (a)
99.3 b)
93 (a)
88 (b)
98.93 (a)
79.9 (b)

99.8
94
99
99.2 (a)
99 (b)
93 (a)
85 (b)
98.5 (a)
81.2 (b)

56
42
0
52

75
60
0
73

35
0
0
36.2

45.45
0
0
42.8

b1
4.5
1
b1

b1
1.2
1
b1

40

60

4.8

1.6

100

Time (min)
Blue S-GLD 150
dye solution

Dye

BNR

Black Novacron R
dye solution

Fig. 6. Variation of the permeate ow as a function of the time for different efuents
[TMP = 10 bar; T = 25C].

CF
CL

NF: Nanoltration treatment; CF: Coagulation/Flocculation treatment; CL: Commercial

Laccase treatment, (a): at = 593 nm, (b): at = 400 nm.

36

I. Khouni et al. / Desalination 268 (2011) 2737

Fig. 8. Treatment of reconstituted dye efuents (A): Reconstituted BB150 efuent, (B): Reconstituted BNR efuent, (a): after CF treatment at the optimum conditions, (b): after CL
treatment at the optimum conditions (C): after NF process treatment.

Tavares et al. [55] showed also the generation of a light orange colour
formed during the degradation of reactive blue 114 (Levax Brilliant
Blue E-BRA) by a CL. Likewise, Sugano et al. [56] showed the
generation of light red-brown reaction products during the decolourization of reactive black 5 by versatile peroxidase.
Moreover, laccase has a negative effect on the characteristics of the
solutions treated; indeed, addition of CL has increased the COD and
the conductivity whether for RDE or for ADS.
In fact, the highest COD retention is obtained by applying the NF
process, whereas CL is not able to remove the COD of samples treated.
On the other hand, synthetic efuents treated by NF were more stable
to light than those treated by CL; laccase efuent catalysis was
oxidized as a function of time. On the other hand, CF treatment
removes also the COD with moderate rates but has no effect on the
conductivity and increase the efuent turbidity. Although, CF
treatment is economically feasible (but sometimes becomes expensive due to the cost of chemicals) with satisfactory dyes removal, its
main drawback is that the nal product is a concentrated sludge
produced in large quantities and removal is pH dependent [57]. This
process is not good for highly soluble dyes and the result with azo,
reactive, acid and especially the basic dyes [58,59] are generally low.
Thus, CF process was widely employed as pre-treatment for the
decolourization of dye wastewater [60]. Finally, obtained results
showed that NF may be the appropriate choice to treat textile dyeing
efuents. Indeed, NF has been proved an efcient process to remove
dyes from both RDE and ADS with moderate COD removal at about
50% with RDE (about 70% with ADS) and with turbidity always b 1
NTU.
4. Conclusion
The present study deals with the decolourization of two types of
synthetic textile dye efuents (RDE and ADS) using coagulation/
occulation, commercial laccase and NF processes.
During coagulation/occulation PAS and CHT-Flocculant CV are
found to be the best among other coagulants and occulants used
resulting in 94% colour removal (for both ADS and RDE) and 42% COD
reduction for reconstituted BB150 efuent (60% for ADS) and in 93% at
593 nm (88% at 400 nm) colour removal and 40% COD reduction for
reconstituted BNR efuent (60% for ADS). However, CF treatment has
increased the turbidity of solutions treated and has no effect on
salinity removal.
In the other hand, the decolourization of reconstituted BB150 and
BNR dye efuents by enzymatic catalysis using commercial laccase
was optimized leading to dye catalysis above 98%. Highest colour
removal was achieved at 98.93%, 79.9%, and 98.9% respectively for the
reconstituted BNR dye efuent at 593 nm and at 400 nm and for the
reconstituted BB150 dye efuent at 620 nm. These results show that
laccase has a strong potential to degrade the textile dyes and resolve
the problem of unnecessary dyes present in the textile industries

efuents. In spite of improvement in colour removal, application of

enzymatic treatment has no effect on COD removal and on salinity
retention of solutions treated.
Finally, for direct NF, the average removals of colour and COD were
respectively about 99.6% and 56% for reconstituted BB150 efuent and
respectively about 99.4% at 593 nm (99.3% at 400 nm) and 52% for
reconstituted BNR efuent. Besides this, contrary to CF and to CL
treatments, permeates obtained by NF process have turbidity
constantly b1. However, NF has a percent of conductivity retention
of about 35% for reconstituted BB150 efuent (45.45% for ADS) and
about 36.2% for reconstituted BNR efuent (42.8% for ADS). The
results of this study show that NF process seems to be an efcient
method for the treatment of textile wastewater in term of decolourization but moderate rates of COD retention were observed. Yet in
order to reuse treated efuents, combination of NF with other types of
treatment such as biological treatment results in very high quality of
treated water in term of COD retention. In addition, combination of NF
with Osmosis Inverse seems to be an appropriate technique to textile
wastewater reuse after removing salinity.
Acknowledgement
The authors wish to thank the staff of the textile industry SARTEX we
are working with for providing us the dyes and the chemicals as well as
for their kind assistance and the fruitful discussions on wastewater
generated from their factory.
References
[1] J.H. Weisburger, Comments on the history and importance of aromatic and
heterocyclic amines in public health, Mutat. Res. 506/507 (2002) 920.
[2] S. Sen, G.N. Demirer, Anaerobic treatment of real textile wastewater with a
uidized bedreactor, Water Res. 37 (2003) 18681878.
[3] C. Hessel, C. Allegre, M. Maisseu, F. Charbit, P. Moulin, Guidelines and legislation.
Review for dye house efuents, J. Environ. Manage. 83 (2) (2007) 171180.
[4] V.A. Shenai, Azo dyes on textiles vs. German ban: an objective assessment. Part III.
Another study, Colourage XLIII. 8 (1996) 4146.
[5] J.C. Greene, G.L. Baughman, Effects of 46 dyes on population growth of fresh green
algae Selenastrum capricornutum, Text. Chem. Color. 28 (1996) 2330.
[6] M.M. Aslam, M.A. Baig, I. Hassan, I.A. Qazi, M. Malik, H. Saeed, Textile wastewater
characterization and reduction of its COD and BOD by oxidation, EJEAF Che 3
(2004) 804811.
[7] C. Allegre, P. Moulin, M. Maisseu, F. Charbit, Savings and re-use of salts and water
present in dye house efuents, Desalination 162 (2004) 1322.
[8] V. Lopez-Grimau, M.C. Gutierrez, Decolourization of simulated reactive dye bath
efuents by electrochemical oxidation assisted by UV light, Chemosphere 62
(2006) 106112.
[9] B. Marrot, N. Roche, Wastewater treatment and reuse in textile industries, a
review, Res. Adv. Water. Res. 3 (2002) 4153.
[10] O.J. Hao, H. Kim, P.C. Chiang, Decolorization of wastewater, Crit. Rev. Environ. Sci.
Technol. 30 (4) (2000) 449505.
[11] S. Mohanty, N.N. Rao, P. Khare, S.N. Kaul, A coupled photocatalytic-biological
process for degradation of 1-amino-8naphthol-3, 6-disulfonic acid (H-acid),
Water Res. 39 (2005) 50645070.
[12] N.N. Rao, G. Bose, P. Khare, S.N. Kaul, Fenton and electro-Fenton methods for
oxidation of H-acid and Reactive Black 5, J. Environ. Eng. 132 (2006) 367376.

I. Khouni et al. / Desalination 268 (2011) 2737

[13] O. Marmargne, C. Coste, Colour removal from textile plant efuents, Am. Dye. Rep.
(1996) 1521.
[14] S. Kim, C. Park, T.H. Kim, J. Lee, S.W. Kim, COD reduction and decolourization of
textile efuent using a combined process, J. Biosci. Bioeng. 95 (2003) 102105.
[15] C. Allegre, P. Moulin, M. Maisseau, F. Charbit, Treatment and reuse of reactive
dyeing efuents, J. Membr. Sci. 209 (2006) 1534.
[16] M.H. Al-Malack, G.K. Anderson, Coagulation-crossow microltration of domestic
wastewater, J. Membr. Sci. 121 (1996) 5970.
[17] P.T. Spicer, S.E. Pratsinis, Shear-induced occulation: the evolution of oc
structure and the shape of the size distribution at steady state, Water Res. 30
(1996) 10491056.
[18] B. Heinzmann, Improvement of the surface water quality in the Berlin region,
Water Sci. Technol. 38 (1998) 191200.
[19] T. Nandy, S. Shastry, P.P. Pathe, S.N. Kaul, Pre-treatment of currency printing ink
wastewater through coagulationocculation process, Water Air Soil Pollut. 148
(2003) 1530.
[20] C. Desjardins, B. Koudjonou, R. Desjardins, Laboratory study of ballasted
occulation, Water Res. 36 (2002) 744754.
[21] S. Elmaleh, H. Yaki, J. Coma, Suspended solids abatement by pH increaseupgrading
of an oxidation pond efuent, Water Res. 30 (1996) 23572362.
[22] S. Rohrsetzer, I. Psazli, F. Csempesz, Colloid stability of electrostatically stabilized
sols. Part III. The role of pH in hydration coagulation and peptization of SiO2- and
Al2O3-sols, Colloid Polym. Sci. 276 (1998) 260266.
[23] M. Syu, B.J. Chen, S.T. Chou, Astudy on the sedimentation model and neutral
network online adaptive control of a benzoic acid imitated wastewater oxidation
process, Ind. Eng. Chem. Res. 42 (2003) 68626871.
[24] J.R. Dominguez, J.B. De Heredia, T. Gonzalez, F. Sanchez-Lavado, Evaluation of
ferric chloride as a coagulant for cork processing wastewaters. Inuence operation
conditions removal organic matter settleability parameters, Ind. Eng. Chem. Res.
44 (2005) 65396548.
[25] M. Rossini, J.G. Garrido, M. Galluzzo, Optimization of the coagulationocculation
treatment: inuence of rapid parameters, Water Res. 33 (1999) 18171826.
[26] A. Gurse, M. Yalcin, C. Dogar, Removal of Remazol Red RB by using Al(III) as
coagulant-occulant: effect of some variables on settling velocity, Water Air Soil
Pollut. 146 (2003) 297318.
[27] J.M. Coulson, J.F. Richardson, J.R. Backhurst, J.H. Harker, Chemical Engineering:
Solutions to the Problems in Chemical Engineering, 5th ed. ButterworthHernemann, Oxford, 2002.
[28] K. Zhu, M.G. El-Din, A.K. Moawad, D. Bromley, Physical and chemical processes for
removing suspended solids and phosphorus from liquid swine manure, Environ.
Technol. 25 (2004) 11771187.
[29] J.P. Wang, Y.Z. Chen, X.W. Ge, H.O. Yu, Optimization of coagulationocculation
process for a paper-recycling wastewater treatment using response surface
methodology, Colloids Surf. Physicochem. Eng. Aspects 302 (2007) 204210.
[30] D. Wesenberg, I. Kyriakides, S.N. Agathos, White-rot fungi and their enzymes for
the treatment of industrial dye efuents, Biotechnol. Adv. 22 (2003) 161187.
[31] J. Karam, J.A. Nicell, Potential applications of enzymes in waste treatment, J. Chem.
Tech. Biotechnol. 69 (1997) 141153.
[32] S. Rodrguez Couto, M. Sanromn, G.M. Gbitz, Inuence of redox mediators and
metal ions on synthetic acid dye decolourization by crude laccase from Trametes
hirsuta, Chemosphere 58 (2005) 417422.
[33] E. Abadulla, T. Tzanov, S. Costa, K.H. Robra, A. Cavaco-Paulo, G.M. Gbitz,
Decolourization and detoxication of textile dyes with laccase from Trametes
hirsuta, Appl. Environ. Microbiol. 66 (2000) 33573362.
[34] M. Morita, R. Ito, T. Kamidate, H. Watanabe, Kinetics of peroxidase catalyzed
decoloration of orange II with hydrogen peroxide, Text. Res. J. 66 (1996) 470473.
[35] L. Setti, S. Giuliani, G. Spinozzi, P.G. Pifferi, Laccase catalyzed-oxidative coupling of
3-methyl 2-benzothiazolinone hydrazone and methoxyphenols, Enzyme Microb.
Technol. 25 (1999) 285289.
[36] A. Sungpet, R. Jironatananon, P. Luangsowan, Treatment of efuents from textilerinsing operations by thermally stable nanoltration membranes, Desalination
160 (2004) 7581.

37

[37] S. Chakraborty, M.K. Purkait, S. Dasgpta, S. De, J.K. Basu, Nanoltration of textile
plant efuent for color removal and reduction in COD, Sep. Purif. Technol. 31
(2003) 141151.
[38] O. Marmagne, C. Coste, Color removal from textile plant efuents, Am. Dyestuff.
Rep. 85 (1996) 1521.
[39] M. Marcucci, G. Nosenzo, L. Ciabatti, D. Corrieri, G. Ciardelli, Treatment and reuse
of textile efuents based on new ultraltration and other membrane technologies,
Desalination 138 (2001) 7582.
[40] C. Fersi, L. Gzara, M. Dhahbi, Treatment of textile efuents by membrane
technologies, Desalination 185 (2005) 18251835.
[41] C. Jarusutthirak, S. Mattaraj, R. Jiraratananon, Inuence of inorganic scalants and
natural organic matter on nanoltration membrane fouling, J. Membr. Sci. 287
(2007) 138145.
[42] A.I. Schfer, A.G. Fane, T.D. Waite, Nanoltration, nanoltration- Principles and
Applications, Elsevier Ltd, UK, 2005 1-85617-405-0.
[43] F. Harrelkas, A. Azizi, A. Yaacoubi, A. Benhammou, M.N. Pons, Treatment of textile
dye efuents using coagulationocculation coupled with membrane processes
or adsorption on powdered activated carbon, Desalination 235 (2009) 330339.
[44] I. Khouni, B. Marrot, R. Ben Amar, Decolourization of the reconstituted dye bath
efuent by commercial laccase treatment: Optimization through response surface
methodology, Chem. Eng. J. 156 (2010) 121133.
[45] G.E.P. Box, K.B. Wilson, On the experimental attainment of optimum condition,
J. R. Stat. Soc. B. 13 (1951) 138.
[46] M. Evans, Optimization of Manufacturing Processes: A Response Surface
Approach, Carlton House Terrace, London, 2003.
[47] D. Mathieu, J. Mony, R. Pan-Tan-Luu, Laboratoire ractionnelle et d'analyse de
l'information, NemrodW Version 2000, Aix en Provence, France, 2000.
[48] M. Muthukumar, D. Mohan, M. Rajendran, Optimization of mix proportions of
mineral aggregates using BoxBehnken design of experiments, Cem. Concr.
Compos. 25 (2003) 751758.
[49] K.Y. Benyounis, A.G. Olabi, M.S.J. Hashmi, Effect of laser welding parameters on the
heat input and weld-bead prole, J. Mater. Proc. Technol. 164/165 (2005) 978985.
[50] Standard Methods for the Examination of Water and Wastewater, 18th
edAmerican Public Health Association/American Water Works Association/
Water Environment Federation, Washington, DC, 1998.
[51] F. Wei, Analysis of Water and Wastewater, Chinese Environmental Science Press,
Beijing, 2002.
[52] D.C. Montgomery, Design and Analysis of Experiments, Third ed.Wiley, New York,
1991.
[53] E. Rodriguez, M.A. Pickard, R. Vazquez Duhalt, Industrial dye decolorization by
laccases from ligniolytic fungi, Curr. Microbiol. 38 (1999) 2732.
[54] M. Chivukula, V. Renganathan, Phenolic azo-dye oxidation by laccase from
Pyricularia oryzae, Appl. Environ. Microbiol. 61 (1995) 43744377.
[55] A.P.M. Tavares, R.O. Cristvo, J.M. Loureiro, R.A.R. Boaventura, E.A. Macedo,
Application of statistical experimental methodology to optimize reactive dye
decolourization by commercial laccase, J. Hazard. Mater. 162 (2-3) (2009) 12551260.
[56] Y. Sugano, Y. Matsushima, M. Shoda, Complete decolorization of the anthraquinone dye Reactive blue 5 by the concerted action of two peroxidises from
Thanatephorus cucumeris Dec1, Appl. Microbiol. Biotechnol. 73 (2006) 862871.
[57] J.W. Lee, S.P. Choi, R. Thiruvenkatachari, W.G. Shim, H. Moon, Evaluation of the
performance of adsorption and coagulation processes for the maximum removal
of reactive dyes, Dyes Pigm. 69 (2006) 196203.
[58] F.I. Hai, K. Yamamoto, K. Fukushi, Hybrid treatment systems for dye wastewater,
Crit. Rev. Env. Sci. Technol. 37 (2007) 315377.
[59] C. Raghavacharya, Colour removal from industrial efuents a comparative review
of available technologies, Chem. Eng. World. 32 (1997) 5354.
[60] B. Shi, G. Li, D. Wang, C. Feng, H. Tang, Removal of direct dyes by coagulation: the
performance of preformed polymeric aluminium species, J. Hazard. Mater. 143
(2007) 567574.