Separation and Purification Technology 55 (2007) 117–124

Separation of methylene blue from aqueous solution

by micellar enhanced ultrafiltration
Narjess Zaghbani, Amor Hafiane, Mahmoud Dhahbi ∗
Laboratoire Eau et Technologies Membranaires, Centre de Recherche sur les Technologies des Eaux,
BP 273, Soliman 8020, Tunisia
Received 31 July 2006; received in revised form 12 November 2006; accepted 12 November 2006

Abstract
Micellar enhanced ultrafiltration (MEUF) is a separation technique which can be used to remove metals ions or dissolved organics from water. In
this study MEUF has been carried out to investigate the retention of metylene blue (MB), a cationic dye, from aqueous stream. Regenerated cellulose
membrane of molecular weight cut-off 10 kDa was used in a cross-flow ultrafiltration unit. Sodium dodecylsulfate (SDS), hexadecyltrimethyl
ammonium bromide (CTAB) and triton X-100 (TX-100) were used as surfactants and NaCl as an electrolyte. The removal of MB and permeate
flux were studied as a function of dye and surfactant concentrations, nature of surfactant, ionic strength and pH.
The ultrafiltration experiments showed that anionic surfactant SDS allowed best rejection of methylene blue (R > 97%) for the used range of dye
and surfactant concentrations. High retention was also obtained at pH range from 2 to 11. Permeate flux decreases when surfactant or electrolyte
concentration increases due mainly to polarisation concentration, osmotic pressure and precipitation.
Prior to MEUF experiments the effect of surfactant type and electrolyte concentration on the spectra of methylene blue has been investigated in
the submicellar and micellar concentration range.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Methylene blue; Micelles; Ultrafiltration; Sodium dodecylsulfate

1. Introduction Micellar enhanced ultrafiltration (MEUF) is one of the pos-

Many industrial processes use different synthetic chemical
dyes for various purposes. Effluents coming out from these
industries are highly coloured, resulting in major environmental
problems. So these coloured wastes need to be treated before
disposal. This is important to regions where water resources
might be scarce or sensitive to the maintenance of ecosys-
tem. Many methods are available for the removal of pollutants
from water, the most important of which are biodegradation [1],
flocculation-coagulation [2], oxidation [3] and adsorption [4].
Recently membrane separation technologies have been used for
the separation of dyes [5,6]. Among membrane processes, the
nanofiltration is the most suitable for the decolourisation of efflu-
ent textile [6]. However, its major disadvantage is the decline in
permeate flux due to adsorption of organic compounds on the
membrane surface [7].
∗ Corresponding author. Tel.: +216 71 43 11 22; fax: +216 71 43 09 34.
E-mail address: mahmoud.dhahbi@inrst.rnrt.tn (M. Dhahbi).
sible methods to remove organic dyes from water. Even though
MEUF method is not yet applied on an industrial scale, many
studies have shown that it is a suitable method for the retention
of metal ions [8,9], anions [10] and organic pollutants [11,12]. In
this process, surfactant with higher concentration than the criti-
cal micelle concentration (CMC) is added to a polluted aqueous
solution. The surfactant molecules form micelles, which can sol-
ubilized, the organic or inorganic contaminants. The micelles
containing the dissolved solutes are rejected during ultrafiltra-
tion process by the membrane and a permeate stream passing
through the membrane is nearly free from impurities.
In the present study methylene blue (MB) is selected as model
compound in order to evaluate the efficiency of MEUF for the
removal of dye from its aqueous solutions. MB has wide appli-
cations, which include colouring paper, temporary hair colorant,
dyeing cottons, wools and coating for paper stock. MB is a thi-
azine cationic dye used as an oxidation-reduction indicator and
in the trace analysis of anionic surfactant. Also, it is used as
antiseptic and for other medicine purposes.
It is well known that surfactants above or below their
critical micellar concentration affect the electronic absorption

1383-5866/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.11.008
118 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124
of solutions of many dyes [13–15]. Hence, it is necessary to
investigate the effect of surfactant solutions on the spectra of
MB before its analysis. The spectral changes of a dye, observed
in the presence of varying amount of surfactants, are consistent
with sequential equilibria involving surfactant monomers,
micelles, dye aggregates, premicellar dye-surfactant complex
and dye incorporated to micelle [16–18].
The objectives of this paper are to study the effect of the
presence of surfactant on the visible spectra of MB and the
effectiveness of MEUF for the removal of methylene blue. The
system variables studied include, surfactant type and concentra-
tion, ionic strength and solution pH.
2. Experimental
2.1. Materials
Methylene blue chloride MB (97% purity) (Fig. 1), sodium
dodecylulfate SDS (98% purity), cetyltrimethylammonium bro-
mide CTAB (99%purity), triton X-100 (TX-100) and sodium
chloride NaCl (99.5% purity) were supplied by Fluka. They were
used without further purification. In all experiments distilled
water was used.
Critical micelle concentrations of the studied surfactants in
distilled water were 0.96, 8 and 0.24 mM for CTAB, SDS and
TX-100, respectively [19].
2.2. Procedure
Ultrafiltration experiments were carried out using a cross-
flow Minitan-S unit purchased from Millipore. A schematic
diagram of the ultrafiltration system is shown in Fig. 2. Organic
Fig. 1. The structure of Methylene blue.
Fig. 2. Schematic of the experimental set up.
regenerated cellulose membrane (PLGC Millipore) of molec-
ular weight cut-off 10 kDa and an effective area of 30 cm2
was used for all the MEUF experiments. The membrane was
soaked in deionised water during 24 h in order to eliminate
preservative products then pure water permeability Lp was
determined. In all experiments, a transmembrane pressure of
1.4 bar was maintained. The feed temperature was set at 30 ◦ C.
The feed tank was initially filled with 200 mL solution and a
micro pump with a variable flow rates was used to feed the
solution into the cell. The retentate as well as the permeate
were recycled in to the feed tank. After nearly 30 min a steady
state was reached and a permeat of 10 mL was collected and
analyzed.
After each run, the membrane was thoroughly washed by dis-
tilled water for at least 15 min and at a pressure of 1.4 bar. The
membrane permeability was checked to ensure that the perme-
ability remains almost constant between successive runs. The
filtration efficiency in removing the dye from the feed solution
was evaluated through the dye rejection which was calculated
using the classical rejection coefficient:
 
Cp
R(%) = 1 − × 100 (1)
C0
where C0 is the initial concentration of the dye in the feed
solution and Cp is the dye concentration in the permeate.
2.3. Determination of methylene blue content
Visible absorption spectra were recorded with a Perkin-Elmer
Lambda 20 spectrophotometer using a matched pair of glass
cuvettes with 1 cm optical lengths. Concentrated stock solu-
tions (10 mM) of the dye were prepared by dissolving weighed
amounts in distilled water, the working solutions were then pre-
pared by dilution.
In the presence of SDS (see Section 3.1), below the CMC,
the MB absorbance varied with the surfactant concentration and
electrolyte content while it remains almost constant at SDS con-
centration above the CMC. The maximum of absorption shifted
slightly from 665 to 663 nm when the concentration of SDS
exceeds 4 mM. Consequently, we have adjusted the concentra-
tion of surfactant in the samples and in the standard solutions
to a value well above CMC in order to analyze MB in pres-
ence of SDS. The MB was analyzed at 663 nm. The effect of
CTAB, TX-100 and pH in the range of 2–11 on the absorbance
of MB was almost negligible. In these cases MB was analyzed at
665 nm. The MB absorbance versus concentration plot follows
Lambert-Beer law from 0 to 8 ␮M in all cases.
3. Results and discussion
3.1. UV–visible study
3.1.1. UV–visible spectra of methylene blue in presence of
SDS
Fig. 3(a) shows the visible spectra of aqueous methylene
blue solution at 5 ␮M for several SDS concentrations ranging
 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124 119

Fig. 3. The visible absorption spectra of MB dissolved in aqueous solutions containing 0–18 mM SDS. Concentration of MB is: (a) 5 ␮M (b) 2 ␮M and (c) 8 ␮M.

from 0 to 18 mM. In aqueous solution ([SDS] = 0 mM) methy-
lene blue presents a maximum absorption at 665 nm and a
shoulder at 612 nm. This observation is consistent with litera-
ture reports [20,21]. As SDS concentration increased gradually
the monomer dye absorbance decreased, the absorbance at the
shoulder decreased weakly. At 4 mM of SDS the absorbance
reached a minimum and a new band appeared at 610 nm. This
band may be attributed to dimerisation leading to H-type aggre-
gation of the dye molecules assisted by the surfactant chain. H
aggregates are spectroscopic entities that are characterised by
a blue-shifted adsorption with respect to monomer absorption
whereas J aggregates present a red-shifted band. The dimeri-
sation is a well known phenomenon, occurring in concentrated
solution of dyes or induced by its preferential adsorption onto
solid substrate [22] or in the presence of macromolecules such
as DNA [23] and cyclodextrine [24]. In the present case, the for-
mation of ion pair MB-DS reduced the electrostatic interaction
between dye cations and thus enhanced dimerisation by London
dispersion and hydrophobic forces.
As the surfactant concentration increased from 4 to 8 mM,
the absorbance of monomer and dimer increased. This is caused
by two different processes. The first is due to the formation
of SDS premicelles taking up dye molecules; the second is
attributed to the suppression of electrostatic interaction between
dye molecules by more surfactant monomers. At 8 mM of SDS,
which correspond to the CMC, the absorbance reaches its lim-
iting value and all dyes molecules are solubilized into normal
micelles as monomeric molecules.
For MB concentrations of 5 ␮M (Fig. 3a) and 2 ␮M (Fig. 3b)
the dimer band was formed at SDS concentration of 4 mM. At
8 ␮M (Fig. 3c) the dimer band appears at a lower SDS concentra-
tion of 2 mM. As the MB solution is more concentrated the dye
120 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124
Fig. 4. Absorbance of methylene blue as a function of SDS for different MB
concentrations at λ = 663 nm.
requires less quantity of surfactant to form dimer. The change
of the monomer absorbance with SDS (Fig. 4) clearly shows
that above 4 mM of SDS the monomer absorbance increased
progressively and reached a maximum value at 8 mM.
Fig. 5. The visible absorption spectra for 5 ␮M MB dissolved in aqueous solutions containing 0–18 mM SDS at different NaCl concentration (M) of (a) 1 mM (b)
10 mM and (c) 100 mM.
For the three MB concentrations, maximum wavelength λmax
of monomer shifts slightly from 665 to 663 nm when the con-
centration of surfactant exceeds 4 mM. As spectral shifts of λmax
are generally interpreted as polarity changes of the immediate
microenvironment of the chromophore [25], the polarity of the
microenvironment felt by MB ions in premicellar and micellar
region is slightly different from water. It can be concluded that
at least part of the MB monomer is located in water rich stern
layer of the micelle.
3.1.2. Effect of the nature of surfactant on visible spectra of
MB
The variation of the absorbance of MB at 5 ␮M as a function
of cationic (CTAB) and neutral (TX-100) surfactants concen-
trations has also been studied. The UV–visible spectra obtained
show that there is no change on the absorbance of MB when the
concentrations of surfactant TX-100 and CTAB varied on both
sides of CMC. This confirms that the variation in the absorbance
of MB with SDS is due mainly to an electrostatic interaction.
Dye-surfactant interaction in aqueous solutions has been
intensively studied in the literature [14,16,26–28]. It has been
established from the spectral studies that for association between
ionic dyes and ionic surfactants both electrostatic and hydropho-
bic forces are important. The interaction of dyes with oppositely
charged surfactants is mainly coulombic in nature. The inter-
 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124 121

action between dyes and surfactants of same charge occurs if

hydrophobic interaction can overcome electrostatic repulsion
[15]. In the presence of non ionic surfactants only hydropho-
bic interaction occurs and a 1:1 charge transfer complex
may form.
MB does not interact with CTAB because hydrophobic inter-
action is weaker than electrostatic repulsion. The absence of
interaction between MB and TX-100 reported by Bhowmik
et al. [26] indicates that hydrophobic interaction is very
weak.

3.1.3. Effect of ionic strength on visible spectra of MB in

presence of SDS
Fig. 5(a–c) represent the visible spectra of MB at fixed MB
concentration equal to 5 ␮M and different SDS concentrations
ranged from 0 to 18 mM, with NaCl respective concentrations
of 1, 10 and 100 mM.
From figures the concentration of SDS at which dimer
appears or disappears decreases when the concentration of NaCl
increases. At [NaCl] = 10 mM, for example, we can see from
Fig. 5(b) that the dimer band appears at SDS = 1 mM and dis-
appears at SDS = 6 mM. The presence of NaCl enhances the
self-association of dye in aqueous solution as well as adding sur-
factant, lowering temperature or increasing dye concentration
[29]. It has been recognised that increasing salt concentra-
tion causes an increase in the screening factors or effective
dielectric constant and thus it promotes dye dimerisation [21].
On the other hand, increasing NaCl concentration allows the
formation of micelles at lower SDS concentration. This is
known as salt effect [30]. When micelles were formed all ionic
dyes were solubilized at monomer form. The change in the
monomer absorbance with SDS concentration in the absence
and the presence of NaCl is represented in Fig. 6. The monomer
absorbance in all cases decreased first and then it increased
rapidly as the SDS concentration gradually increased. At con-
centrations above the CMC the absorbance remains almost
constant.
Fig. 6. Effect of SDS concentration on the monomer absorbance of MB at
λ = 663 nm for different concentrations of NaCl. Concentration of MB is 5 ␮M.
Fig. 7. (a) Variation of retention of MB with time at different MB concentra-
tions (M) of (♦, ) 0.02 mM, (,  ) 0.1 mM, (, ) 0.5 mM, (, 䊉) 1 mM.
[SDS] = 20 mM; empty (♦, , , ) and full points (, , , 䊉) correspond
to the solutions without and in presence of SDS, respectively. (b) Variation of
permeate flux with time at different MB concentrations (M) of (♦, ) 0.02 mM,
(,  ) 0.1 mM, (, ) 0.5 mM and (, 䊉) 1 mM. [SDS] = 20 mM.; empty (♦,
, , ) and full points (, , , 䊉) correspond to the solutions without and
in presence of SDS, respectively.
3.2. Ultrafiltration study
3.2.1. Ultrafiltration of dye solution with and without
surfactant
Fig. 7(a and b) show, respectively, retention rate of MB
and flux of permeate as a function of time. We observed from
Fig. 7(a) that the retention of MB is negligible in absence of sur-
factant. Since the MB molecules are much smaller than the mem-
brane pores the retention could be attributed to the adsorption of
dye at the surface or in the pores of membrane. When surfactant
is used, the retention of MB increases to about 98%. This clearly
indicates that the dye is solubilized on the surfactant micelles,
which are subsequently retained by the ultrafiltration membrane.
The variation of the permeate flux without surfactant (Fig. 7b)
remains constant with time. However, with the presence of
surfactant a slight decrease of flux is observed during initial
stage of filtration, and thereafter, the flux attains a steady-state
value. Lower flux is observed during UF of dye with surfactant
micelles. During the ultrafiltration, the micelles formed by sur-
factant molecules are rejected and accumulated near the mem-
brane surface, resulting in a higher surfactant concentration near
the membrane compared to the bulk surfactant concentration.
122 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124
Fig. 8. Retention of MB (%) and permeate flux as a function of feed SDS
concentration. [MB] = 0.1 mM.
The data in Fig. 7(b) show that permeate flux, in presence of
surfactant, decreases from 5 to 35% for initial dye concentration
ranging from 10−5 to 10−3 M. Purkait et al. reported similar
trends of permeate flux during cross-flow ultrafiltration of CPC
solution in presence of phenolic derivatives [31] and eosin dye
[32].
3.2.2. Effect of feed surfactant concentration on MB
retention and permeate flux
Fig. 8 describes the effect of feed SDS concentration on the
retention of MB and on steady-state flux at a fixed MB concen-
tration of 0.1 mM.
At SDS concentrations above the CMC the retention of MB
ranged from 94.65% at SDS feed concentration of 8 mM to
97.80% at SDS feed concentration of 18 mM. In these exper-
iments the ratio of SDS to MB are high enough to exceed the
solubilization capacity of the micelles.
For low surfactant concentrations ranging from 0 to 8 mM
at which no micelles are present, MB retention of about 97%
was obtained. This value is too high to be attributed to the
adsorption effect. This result was due to the well known precipi-
tation reaction of MB in the presence of anionic SDS surfactant.
Most of MB being in solid phase will be rejected by the UF
membrane. The precipitation reaction of anionic surfactant with
MB, followed by an extraction with chloroform, was the base
of a standard method for anionic surfactants determination in
water. Recently a multicommutation automated procedure for
the determination of anionic surfactants in water employing the
methylene blue spectrophotometric method has been developed
[33].
The permeate flux, as we can see from Fig. 8, decreases when
the feed surfactant concentration increases. The permeate flux
reduction observed may depend on several phenomena, such
as concentration polarisation, membrane fouling, osmotic pres-
sure, precipitation, formation of a gel layer on the membrane
surface. The experiments in this work were conducted at surfac-
tant concentrations below or slightly above the CMC, which are
likely much smaller than those of which the gel layer may form,
i.e. for ionic surfactants, the gel layer is about 0.6 M [34].
The permeate flux J (m s−1 ) is commonly described by using
a resistance-in-series model of the following form:
P − π
J= (2)
ηRt
Here, P (Pa) is the transmembrane pressure difference, π
(Pa) the osmotic pressure difference across the membrane, Rt
(m−1 ) the total resistance and η (Pa s) is the viscosity of aqueous
solution.
Rt is composed of four resistances as
Rt = Rm + Rcp + Rf + Rc (3)
where Rm is the intrinsic membrane resistance, Rc the cake layer
resistance; Rcp the concentration polarisation resistance and Rf
is the fouling resistance.
Above the CMC surfactant micelles generates a deposited
layer over the membrane surface (concentration polarisation)
and consequently, increases the resistance against the solvent
flux though the membrane. Also, the increases in the osmotic
pressure difference across the membrane (related to the micelle
concentrations in the retentate and permeate) reduces the effec-
tive transmembrane pressure and consequently, decreases the
permeate flux.
Below the CMC the precipitated solids MB-DS are convec-
tively driven during cross-flow filtration to the membrane surface
where they accumulate and tend to form a cake, which provides
an additional resistance to filtration.
3.2.3. Effect of the nature of surfactant
The effect of the nature of the surfactant on the retention of
methylene blue was studied by comparing the filtration of dye
solutions in presence of anionic (SDS), cationic (CTAB) and
nonionic (TX-100) surfactants. The filtrated solutions contain
0.1 mM of MB and 10×CMC of surfactant. The retentions of
MB obtained are 99.45, 2.82, and 2.10% in presence of SDS,
CTAB and TX-100, respectively.
It is evident from the results that MB retention was remark-
able only in presence of the anionic surfactant. It has been
expected that retention of MB by anionic micelles would be
the highest because of the opposite charge of the components.
The absence of retention of MB in presence of CTAB supports
this expectation. The retention of MB in presence of TX-100 is
negligible and indicated that hydrophobic interactions between
the components are insignificant. In conformity with the above
spectroscopic study, the results indicated that the electrostatic
interaction between MB and surfactants played an important
role in the retention.
3.2.4. Effect of ionic strength
The effect of the solution ionic strength was also studied. In
reality, effluents from textile and dyeing industries contain a high
concentration of salts which may affect the removal of dye. An
increase in the ionic strength increased the free counter ion con-
centration, thereby decreasing the energy of repulsion between
charged head group of micelles which induced a decrease in the
CMC and an increase in the aggregation number of micelles.
 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124
Fig. 9. Effect of ionic strength on the MB retention. [MB] = 0.1 mM and
[SDS] = 0–18 mM.
Consequently, the addition of small amounts of electrolyte to
solutions of ionic surfactants increases the extent of solubiliza-
tion of hydrocarbons and decreases that of polar compounds
[35]. In the case of MB, it can be seen from Fig. 9 that MB solu-
bilization, and then retention, increases slightly upon increasing
the sodium chloride concentrations from 0 to 100 mM.
Fig. 10 presenting the variation of permeate flux as a function
of feed concentration of SDS, indicates that the flux of perme-
ate decreased when the concentration of NaCl increased. Thus,
larger fraction of SDS micelles are formed which enhanced the
effect of polarisation concentration and osmotic pressure.
3.2.5. Effect of pH
To study the effect of pH on MB retention, the experiments
were carried out at 0.1 mM initial dye concentration with 50 mM
SDS concentration. The initial pH value ranging from 2 to 11
was controlled by the addition of dilute chloride acid or sodium
hydroxide solutions. Fig. 11 shows that the pH of the medium
did not have any significant effect on retention of MB by MEUF
with pH varying from 2 to 11. The retention is near 99% in the
whole range of pH.
Fig. 10. Effect of ionic strength on the permeate flux. [MB] = 0.1 mM and
[SDS] = 0–18 mM.
123
Fig. 11. Effect of pH on the retention of MB and on the permeate flux.
[MB] = 0.1 mM and [SDS] = 50 mM.
According to the acid-base equilibrium of MB represented
by MBH2+ ↔ MB+ + H+ , and to its very low pKa value (less
than 1) the removal of MB was due mainly to solubilization of
unprotonated form of the dye MB+ . The same result has been
obtained in the case of phenol filtrated in presence of cationic
surfactant CTAB [11]. It was also found that retention of inor-
ganic cations such as Cu2+ [36] or Cd2+ [37] by MEUF were
very sensitive to pH. The sharp decrease obtained in copper and
cadmium removal efficiency below pH 4 and 3 might be due to
the competition between cations and protons to bind to micelles.
The effect of pH on the retention of MB cannot be explained by
an ionic-exchange model, as it is in the case of inorganic ions.
It seems that hydrophobic interactions contribute to the binding
between MB and SDS micelles. Large polar molecules, such as
MB, are believed to be solubilized mainly between the individ-
ual molecules of surfactant in the palisade layer with the polar
groups of the solubilizate oriented toward the polar groups of
the surfactants and the nonpolar portions oriented toward the
interior of the micelle [19].
The effect of pH on the permeate flux has been also stud-
ied. Fig. 11 shows that the flux increased progressively when
pH increased from 2 to11. This can be attributed to the fact
that the membrane becomes more hydrophilic as a result of
deprotonation of carboxylic group within the membrane active
layer.
4. Conclusions
MEUF of MB in SDS solution using10 kDa MWCO mem-
brane has been studied using a cross-flow ultrafiltration cell. The
retention of MB was about 95–99% in the range of 10−2 to 1 mM
dye concentration. The retention depended slightly on the sur-
factant and dye concentrations, ionic strength and pH. This was
due to the strong interaction between SDS and MB. However,
due to polarisation concentration, osmotic pressure and precipi-
tation, the permeate flux decreased when the surfactant and ionic
strength increased.
The preliminary UV–visible spectrometry showed that
anionic surfactant SDS affected the MB spectra. MB forms dim-
124 N. Zaghbani et al. / Separation and Purification Technology 55 (2007) 117–124
mers with SDS in submicellar concentration regions. Beyond
the CMC the dye gradually reverts to the monomer state.
Acknowledgement
The authors wish to acknowledge the funding support of
this study by the Tunisian Ministry of Scientific Research, of
Technology and Competency development.
References
[1] G.M. Walker, L.R. Weatherley, Biodegradation and biosorption of acid
anthraquinone dye, Environ. Pollut. 108 (2000) 219–223.
[2] V. Golob, A. Vinder, M. Simonič, Efficiency of the coagulation/flocculation
method for the treatment of dyebath effluents, Dyes Pigments 67 (2005)
93–97.
[3] A. Roessler, D. Crettenand, O. Dossenbach, W. Marte, P. Rys, Direct elec-
trochemical reduction of indigo, Electrochim. Acta 47 (2002) 1989–1995.
[4] S. Wang, Z.H. Zhu, A. Coomes, F. Haghseresht, G.Q. Lu, The physical and
surface chemical characteristics of activated carbons and the adsorption
of methylene blue from wastewater, J. Colloid Interface Sci. 284 (2005)
440–446.
[5] S. Chakraborty, S. De, J.K. Basu, S. DasGupta, Treatment of a textile
effluent: application of a combination method involving adsorption and
nanofiltration, Desalination 174 (2005) 73–85.
[6] C. Fersi, L. Gzara, M. Dhahbi, Treatment of textile effluents by membrane
technologies, Desalination 185 (2005) 399–409.
[7] B. Van der Bruggen, B. Daems, D. Wilms, C. Vandecasteele, Mechanisms
of retention and flux decline for the nanofiltration of dye baths from the
textile industry, Sep. Purif. Technol. 22–23 (2001) 519–528.
[8] S.D. Christian, J.F. Scamehorn, Surfactant-Based Separation Process:
Surfactant Science Series, vol. 33, Marcel Dekker, New York, 1989,
p. 29.
[9] A. Hafiane, I. Issid, D. Lemordant, Counterion binding on micelles: an
ultrafiltration study, J. Colloid Interface Sci. 142 (1991) 167–178.
[10] L. Gzara, M. Dhahbi, Removal of chromate anions by micellar-enhanced
ultrafiltration using cationic surfactants, Desalination 137 (2001) 241–
250.
[11] H. Adamczak, K. Materna, R. Urbański, J. Szymanowski, Ultrafiltration of
micellar solutions containing phenols, J. Colloid Interface Sci. 218 (1999)
359–368.
[12] S.R. Jadhav, N. Verma, A. Sharma, P.K. Bhattacharya, Flux and retention
analysis during micellar enhanced ultrafiltration for the removal of phenol
and aniline, Sep. Purif. Technol. 24 (2001) 541–557.
[13] M. Sarkar, S. Poddar, Spectral studies of methyl violet in aqueous solutions
of different surfactants in supermicellar concentration region, Spectrochim.
Acta, Part A: Mol. Biomol. Spectrosc. 55 (1999) 1737–1742.
[14] M. Sarkar, S. Poddar, Studies on the interaction of surfactants with cationic
dye by absorption spectroscopy, J. Colloid Interface Sci. 221 (2000)
181–185.
[15] R. Sabaté, M. Gallardo, A. de la Maza, J. Estelrich, A Spectroscopy study of
the interaction of pinacyanol with n-dodecyltrimethylammonium bromide
micelles, Langmuir 17 (2001) 6433–6437.
[16] S. Göktürk, M. Tunçay, Spectral studies of safranin-O in different surfactant
solutions, Spectrochim. Acta, Part A: Mol. Biomol. Spectrosc. 59 (2003)
1857–1866.
[17] R.V. Pereira, M.H. Gehlen, Fluorescence of acridinic dyes in anionic sur-
factant solution, Spectrochim. Acta, Part A: Mol. Biomol. Spectrosc. 61
(2005) 2926–2932.
[18] K.K. Karukstis, D.A. Savin, C.T. Loftus, N.D. D’Angelo, Spectroscopic
studies of the interaction of methyl orange with cationic alkyltrimethylam-
monium bromide surfactants, J. Colloid Inteface Sci. 203 (1998) 157–163.
[19] M.J. Rosen, Surfactants and Interfacial Phenomena, third ed., Wiley-
Interscience, New York, 2004.
[20] E. Rabinowitch, L.F. Epstein, Polymerization of dyestuffs in solution. Thio-
nine and methylene blue, J. Am. Chem. Soc. 63 (1941) 69–78.
[21] P. Mukerjee, A.K. Gosh, Thermodynamic aspects of the self-association
and hydrophobic bonding of methylene blue. A model system for stacking
interactions, J. Am. Chem. Soc. 92 (1970) 6419–6424.
[22] K. Bergmann, C.T. O’Konski, A spectroscopic study of methylene blue
monomer, dimer and complexes with montmorillonite, J. Phys. Chem. 67
(1963) 2169–2177.
[23] L.Z. Zhang, G.Q. Tang, The binding properties of photosensitizer methy-
lene blue to herring sperm DNA: a spectroscopic study, J. Photochem.
Photobiol., B 74 (2004) 119–125.
[24] G. Zhang, S. Shuang, C. Dong, J. Pan, Study on the interaction of methy-
lene blue with cyclodextrin derivatives by absorption and fluorescence
spectroscopy, Spectrochim. Acta, Part A 59 (2003) 2935–2941.
[25] R. Sabaté, M. Gallardo, J. Estelrich, Location of pinacyanol in micellar
solutions of N-alkyl trimethylammonium bromide surfactants, J. Colloid
Interface Sci. 233 (2001) 205–210.
[26] B.B. Bhowmik, M. Mukhopadhyay, Spectral and photophysical studies of
thiazine dyes in triton X-100, Colloid Polym. Sci. 266 (1988) 672–676.
[27] A.K. Jana, S. Rajavenii, Studies on the molecular interaction of phenazine
dyes with Triton X-100, Spectrochim. Acta, Part A 60 (2004) 2093–2097.
[28] D. Pramanick, D. Mukherjee, Molecular interaction of methylene blue with
Triton X-100 in reverse micellar media, J. Colloid Interface Sci. 157 (1993)
131–134.
[29] L. Antonov, G. Gergov, V. Petrov, M. Kubista, J. Nygren, UV–vis spectro-
scopic and chemometric study on the aggregation of ionic dyes in water,
Talanta 49 (1999) 99–106.
[30] M.L. Corrin, W.D. Harkins, The effect of salts on the critical concentration
for the formation of micelles in colloidal electrolytes, J. Am. Chem. Soc.
69 (1947) 683–688.
[31] M.K. Purkait, S. DasGupta, S. De, Micellar enhanced ultrafiltration of
phenolic derivatives from their mixture, J. Colloid Interface Sci. 285 (2005)
395–402.
[32] M.K. Purkait, S. DasGupta, S. De, Removal of dye from wastewater using
micellar enhanced ultrafiltration and recovery of surfactant, Sep. Purif.
Technol. 37 (2004) 81–92.
[33] E.R. Torralba, B.F. Reis, A.M. Rubio, M. de la Guardia, An environmentally
friendly multicommutated alternative to the reference method for anionic
surfactant determination in water, Talanta 66 (2005) 591–599.
[34] E. Fernandez, J.M. Benito, C. Pazos, J. Coca, Ceramic membrane ultra-
filtration of anionic and nonionic surfactant solutions, J. Membr. Sci. 246
(2005) 1–6.
[35] H.B. Klevens, Effect of electrolytes upon the solubilization of hydrocarbons
and polar compounds, J. Am. Chem. Soc. 72 (1950) 3780–3785.
[36] S. Ahmadi, Y.C. Huang, B. Batchelor, S.S. Koseoglu, Binding of heavy
metals to derivatives of cholesterol and sodium dodecyl sulfate, J. Environ.
Eng. 121 (1995) 645–652.
[37] L. Gzara, A. Hafiane, M. Dhahbi, D. Lemordant, Modelisation de la
rétention des ions Cd2+ et Mg2+ par ultrafiltration assistée par les micelles
en milieu acide, Entropie 222 (1999) 28–33.