Journal of Environmental Management 203 (2017) 8e16

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Journal of Environmental Management

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Research article

Application of saponin biosurfactant and its recovery in the MEUF

process for removal of methyl violet from wastewater
Kulbhushan Samal, Chandan Das**, Kaustubha Mohanty*
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, 781039, India

a r t i c l e i n f o a b s t r a c t

Article history: The potential of saponin, a biosurfactant, in the micellar enhanced ultraltration (MEUF) process was
Received 15 May 2017 tested systematically for removal of methyl violet from wastewater. For this, the aqueous extract of
Received in revised form reetha (Sapindus mukorossi) pericarp which contains saponin was used as the biosurfactant. First, the
21 July 2017
micellar solubilization of methyl violet in saponin micelles was investigated in terms of molar solubi-
Accepted 27 July 2017
lization power (SP) of saponin. It was observed that the adsorption of methyl violet on the agglomerates
of saponin micelles was mainly responsible for the enhanced solubilization. The Gibbs free energy of
solubilization (calculated as
29.63 kJ mol
1) suggested that process was feasible and spontaneous. The
Keywords:
Dye removal
MEUF experiments were performed in batch as well as continuous mode using saponin biosurfactant,
Micellar-enhanced ultraltration and the effect of operating parameters on permeate ux and solute retention were evaluated. The
Micellar solubilization removal of methyl violet in MEUF process was >99% achieved with 10 kDa polyethersulfone (PES)
Saponin membrane for feed dye concentration of 250 mg L
1 at studied conditions. Finally, the saponin in
Recovery permeate was recovered using n-heptane and n-butanol by solvent extraction process. The solvent n-
butanol showed better extraction efciency as compared to n-heptane for saponin extraction.
2017 Elsevier Ltd. All rights reserved.

1. Introduction energy consumption as compared to individual membrane pro-

Dyes are one of the major class of pollutants in the aqueous
system coming directly from various industries such as textile,
dyeing, cosmetics, printing, etc. The treatment of dye-
contaminated wastewater has been one of the important environ-
mental problems due to their hazardous nature (Verma et al., 2012;
Salleh et al., 2011). The removal of dyes from the aqueous system
has been studied using various wastewater treatment methods
such as adsorption, biological treatment, ozone treatment, coagu-
lation, photocatalytic degradation processes, chemical oxidation
and membrane processes (Holkar et al., 2016; Brillas and Martnez-
Huitle, 2015; Dasgupta et al., 2015). But, their application is limited
due to their disadvantages such as secondary pollution by
byproduct formation, expensive or inefcient process (Yagub et al.,
2014). On the other hand, the membrane integrated process such as
micellar enhanced ultraltration (MEUF) process has shown ad-
vantages of high removal efciency, high permeate ux, and lower
* Corresponding author.
** Corresponding author.
E-mail addresses: cdas@iitg.ernet.in (C. Das), kmohanty@iitg.ernet.in
(K. Mohanty).
cesses (Shah et al., 2016; Purkait et al., 2004).
The micellar enhanced ultraltration technique utilizes the
binding ability of a surfactant after a certain concentration called
critical micelle concentration (CMC), to increase the hydrodynamic
size of smaller solute so that they can be rejected by an ultral-
tration membrane (Purkait et al., 2004). The micelles of surfactant
containing hydrophobic tail and hydrophilic head have the ability
to bind the solute depending on the nature of solute and surfac-
tant. The MEUF processes have been used frequently for the
removal of various pollutants, such as dyes, heavy metal ions,
pesticides, organic and inorganic compounds from aqueous sys-
tems using different surfactants (Shah et al., 2016; Purkait et al.,
2004). The selection of surfactant is an important aspect of the
MEUF process which depends on the nature of the solute to be
separated. In the past, a numerous anionic surfactants, cationic
surfactants, nonionic surfactants ionic-nonionic mixed surfactants
were used in different MEUF processes (Schwarze, 2017; Das et al.,
2008). Most of them have been chemically synthesized which are
less biodegradable or persistent and may cause chronic toxicity
and estrogenic activity (Pradhan and Bhattacharyya, 2017). In
MEUF, the used surfactant remains in permeate stream at a high
concentration which creates secondary pollution. Therefore,

http://dx.doi.org/10.1016/j.jenvman.2017.07.073
0301-4797/ 2017 Elsevier Ltd. All rights reserved.
 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16
before disposing them to a water body, recovery or removal of
these surfactants from permeate stream is necessary. However,
very few researchers have focused on the recovery of surfactant in
the MEUF process. The surfactants in MEUF were recovered by
integrating various technologies, such as precipitation by counter
ion, lowering the temperature below Kriff pint, foam fractionation
and electrochemical treatment (Purkait et al., 2004; Huang et al.,
2017). But, the application of these processes was limited due to
the complex nature of the process, the lower recovery rate of the
surfactant, inevitable damage to micelle molecules, and reduced
surfactant efciency after recovery.
In contrast to chemically synthesized surfactants, natural sur-
factants such as saponin have gained the signicant interest of
researchers, since it is biodegradable, renewable, environmentally
safe as well as ecologically adaptable (Pradhan and Bhattacharyya,
2017; Schmitt et al., 2014). Saponins are mainly secondary metab-
olite present in various plant fruit seed, pericarp, root, leaf, bark,
and ower. More than 100 families of plants and few marine
sources have been reported for the occurrence of saponins (Cheok
et al., 2014). The Sapindus mukurossi, also known as ritha, reetha or
soapnut is a major source of saponin, is a widely distributed plant in
India and other sub continent of Asia. The previous reports on
saponin were mainly focused on the identication, extraction,
quantication, and characterization of saponin (Cheok et al., 2014;
Bottcher and Drusch, 2017; Li et al., 2013; Heng et al., 2014; Gl-
Ustndag  and Mazza, 2007). Very few literature were found
reporting the application of saponin surfactant in the various pro-
cess such as soil washing (Zhou et al., 2013; Mukhopadhyay et al.,
2015), surfactant enhanced oil recovery (Chhetri et al., 2009), sol-
ubilization of dyes (Samal et al., 2017) and synthesis of nano-
particles (Rao and Paria, 2015), etc. All these studies have
mentioned about the adequate micellar property, solubilization
performance and eco-friendly nature of saponin which motivated
us to utilize it in the MEUF process. Further, the review of the
literature suggested that the utilization of biosurfactant saponin in
MEUF process was unexplored.
The present study demonstrates the application of an eco-
friendly biosurfactant (saponin) in micellar enhanced ultraltra-
tion process for removal of methyl violet dye from wastewater. The
micellar solubilization of methyl violet by saponin micelle was
examined in the aqueous solution of saponin at various saponin
concentrations. The effect of solution pH and the addition of NaCl
salt in surfactant solution on dye solubility was tested. The dye
solubilization capacity of saponin micelle was calculated in terms of
molar solubilization power (SP), partition coefcient (Km). Ther-
modynamic property of solubilization process, the Gibbs free en-
ergy of solubilization (DG) was also calculated. The micelle shape
was observed under an optical microscope, and the size of saponin
micelle and dye solubilized micelle were measured. The feasibility
of MEUF process using saponin as a surfactant was tested in a dead
end batch cell using polyethersulfone (PES) membranes of different
molecular weight cut-off (MWCO). The initial trials were done to
investigate the effect of a change in saponin and dye concentration,
transmembrane pressure drop, pH, NaCl salt concentration on
permeate ux, dye and saponin retention. Then, for an extended
operation and continuous separation, the MEUF experiments were
performed in the continuous cross ow cell, in full recycle mode.
The variation in permeate ux and solute retention with cross ow
velocity, transmembrane pressure drop, and feed composition were
evaluated. The recovery of surfactant is an important aspect of any
MEUF process; therefore, recovery of saponin was also attempted
by solvent extraction process using n-heptane and n-butanol as a
solvent.
9
2. Materials and methods
2.1. Chemicals
Methyl violet (C25H30ClN3; MW: 407.99; lmax: 571 nm) was
procured from HiMedia Laboratories Pvt. Ltd., India. Saponin puri-
ed was obtained from Loba Chemie, India, reetha fruits were
collected from local market of Basna, India. The other chemicals,
such as NaCl (Merck, India), NaOH (Rankem, India) and HCl (Ran-
kem, India), n-heptane (Merck, India), n-butanol (Merck, India)
were used as received. Deionized water was used as a solvent for all
the experiments. The synthetic feed was prepared by dissolving an
appropriate amount of dye in water.
2.2. Membranes
The at sheet polyethersulfone (PES) membranes having MWCO
of 10, 20, 30, and 50 kDa were purchased from M/s Permionics
Membranes Pvt. Ltd., Gujarat, India and used without any further
modication. Each fresh membrane was compacted using deion-
ized water at a pressure of 500 kPa for 4 h before utilized in the
experiments. The membrane permeability was calculated using the
standard procedure to be 3.81  10
11 m s
1 Pa
1,
4.97  10
11 m s
1 Pa
1, 7.61  10
11 m s
1 Pa
1, 1  10
10 m s
1
Pa
1 for membrane MWCO of 10, 20, 30, and 50 kDa respectively.
2.3. Biosurfactant
The biosurfactant saponin was extracted from the pericarp of
dried reetha (Sapindus mukorossi) fruit using water as a solvent and
used in the MEUF experiments. The extraction of saponin from
reetha pericarp and its characterization is reported in our previous
work Samal et al. (2017). The aqueous reetha was used as surfactant
solution, and it is termed as aqueous reetha solution (ARS) in this
report.
2.4. Experimental setup
2.4.1. Batch cell
The unstirred batch experiments were conducted in 350 mL
ultraltration batch cell which can accommodate a membrane over
a base support having a diameter of 80 mm. The effective mem-
brane area was 4.3  10
3 m2. The cell was equipped with a
compressor for pressurizing the cell.
2.4.2. Cross-ow cell
A rectangular cross ow membrane module was fabricated with
the help of mechanical engineering workshop, IIT Guwahati. The
design of cross-ow membrane module and the experimental
setup was similar as reported by Das et al. (2006). The effective
membrane surface area of cross-ow cell was 1.64  10
2 m2.
2.5. Experiments
2.5.1. Micellar solubilization
Batch micellar solubilization experiments were carried out by
dissolving methyl violet in saponin solution of known concentra-
tion (200 mg L
1 to 10,000 mg L
1) in 30 mL screw capped vials.
The effect of pH and NaCl concentration on micellar solubilization
of methyl violet was examined within the pH range of 3.0e12.5 and
NaCl salt concentration range of 10e50 g L
1 respectively. The
saponin micelles and its agglomerates were observed using an
optical microscope. The solubilized methyl violet in agglomerates
of saponin micelles was also noticed. The particle size of micellar
saponin and methyl violet solubilized micelles were measured. The
10 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16
experimental procedure of solubilization of methyl violet dye in
saponin micelles was similar to our previous work Samal et al.
(2017) described for solubilization of methylene blue and eosin
yellow. The solubilization capacity of methyl violet in saponin mi-
celles was measured in terms of solubilization power and calcu-
lated using equation (1). The partition coefcient of methyl violet
between the aqueous solution and saponin micelles was evaluated
using equation (2). The Gibbs free energy of solubilization was
calculated using equation (3).
Sdye
SCMC
SP
Csurfactant
CMC
SP
Km
SCMC   Vw  1 SP
DG
RT ln Km
where Sdye and SCMC are the solubilized methyl violet in the solution
at saponin concentration and CMC respectively. Csurfactant is saponin
concentration in the solution, and CMC is the critical micellar
concentration of saponin, Vw is the molar volume of water, R is the
gas constant, and T is the temperature.
2.5.2. Micellar-enhanced ultraltration
2.5.2.1. Batch-mode. The membrane ltration experiments were
carried out with aqueous methyl violet solution and the mixture of
saponin and methyl violet in an unstirred batch cell. The effect of
solution pH, membrane MWCO, NaCl concentration, saponin e
methyl violet ratio in feed and the transmembrane pressure drop
on the permeate ux along with the retention of dye and saponin
were examined. The operating parameters of unstirred batch cell
experiments are described in Table 1. The batch cell experiments
were performed at room temperature (27 3  C). The compacted
membrane was placed inside the cell on a porous support then the
cell was lled with the feed solution. The compressor was operated
to attain the desired pressure. Permeate was collected from the
bottom outlet of the cell during the experiment and the permeate
ux was calculated using equation (4). The experiments were
performed for a duration of 60 min, and sample permeate was
collected at the different time interval for analysis. After that
pressure of compressor was released. After one set of the experi-
ment, the membrane was taken off from the cell carefully and
cleaned with deionized water. The washed membrane was used
again in consecutive runs after getting an adequate permeability.
Methyl violet and saponin retention (Ro) was calculated using
equation (5).
Vp
Permeate Flux
T Am
Table 1
Operating conditions of batch cell and cross ow cell MEUF experiments.
S. No. Parameter
1 Methyl violet (mg L
1) concentration
2 Saponin concentration (mg L
1)
3 Membrane MWCO (kDa)
4 Operating pressure (kPa)
5 pH
6 NaCl concentration (g L
1)
7 Cross ow rate (LPM)
 
Cp
Ro 1
(5)
Co
where Vp is the cumulative volume of permeate collected in a time
duration of T, Am is the area of the membrane, Cp is the solute
concentration in permeate and Co is the solute concentration in
feed.
2.5.2.2. Continuous cross ow mode. MEUF experiments using
saponin as the surfactant was conducted in a cross-ow cell. The
(1)
effect of various parameters such as cross ow rate, trans-
membrane pressure drop and concentrations of surfactant and dye
were examined. The experiments were carried out with 10 kDa
(2) membrane at room temperature (27 3  C). The operating condi-
tions of cross-ow membrane ltration experiments are given in
Table 1. The experiments were conducted following the procedure
(3) described by Das et al. (2006). The Cumulative volumes of
permeate were collected for a duration of 40 min, and the permeate
ux was calculated. Permeate samples were collected after
different time interval for dye and surfactant concentration
analysis.
2.5.3. Recovery of surfactant
The solvent extraction method was used for recovery of the
saponin from permeate stream. Two solvent n-butanol and n-
heptane were tested as a solvent for the extraction of saponin from
aqueous streams at room temperature (27 3  C). The batch ex-
periments were performed by mixing different volume of n-
butanol or n-heptane, such as 2, 4, 6, 8 and 10 mL with xed volume
(10 mL) of saponin solution having a concentration of 350, 8000,
2000 and 5000 mg L
1. This mixture was vigorously mixed for
15 min at 500 rpm to achieve the equilibrium separation. The sol-
vent phase was then separated from the aqueous phase carefully,
and concentration of aqueous phase was measured.
2.6. Analysis
Saponin and methyl violet concentration were analyzed by a UV
spectrophotometer (Thermo Scientic, Germany; SPECTRASCAN
UV-2700). The samples were diluted with deionized water as per
the requirement of UV spectrophotometer analysis, and then the
original concentration was calculated. The concentration was
measured simultaneously in mix component mode. The maximum
absorbance lmax value for saponin was 267 nm, and 571 nm for
methyl violet. The shape of saponin micelles/agglomerates was
observed using an optical microscope (Leica, TM700, Germany).
The particle size of saponin micelle/agglomerates and solubilized
methyl violet in micelles/agglomerates were analyzed by using
(4) Beckman Coulter, DelsaTm Nano C, Germany. The surface
morphology of fresh membrane and after use in MEUF process was
observed using FE-SEM (Zeiss, Sigma, USA).
Operating conditions
Batch cell Cross ow cell
200 and 250 200 and 250
2000, 3000, 5000 and 10,000 2000, 3000, 5000 and 10,000
10, 20, 30 and 50 10
150, 200, 250, 300, 350, 400, 450 and 500 150, 200, 250, 300 and 350
2.5, 4.5, 6.5, 8.5, 10.5 and 11.5 6.5
10, 30, 50 e
e 0.5, 0.6, 0.8, 1.0, 1.2
 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16
3. Results and discussion
3.1. Micellar solubilization of methyl violet
The effect of saponin concentration on the micellar solubiliza-
tion of methyl violet was examined at various concentrations of
saponin. The amount of solubilized methyl violet for a saponin
concentration in the solution is plotted in Fig. 1(a). With increasing
surfactant concentration in the solution, solubilized methyl violet
concentration was increased above the CMC of surfactant. The
enhancement in the solubility of methyl violet with growing
saponin concentration in the solution was due to the incorporation
of dyes into the micelles of surfactant. The increased solubilization
was the resultant of micellar solubilization of dye in saponin mi-
celles and solubilization of dye on the agglomerates of saponin
micelles (Samal et al., 2017). The molar solubilization power (SP)
was calculated as 0.351 mM of dye per mM of saponin. For the
practical application, molar solubilization power can be repre-
sented as mass solubilization power. The mass solubilization power
Fig. 1. Solubilized methyl violet: (a) effect of saponin concentration in the solution; (b) effect of solution pH; (c) effect of NaCl concentration in the solution.
11
was calculated to be 0.143 mg L
1 of dye per mg L
1 of saponin. The
solubilization power (SP) and ln Km value were measured as
0.351 mM mM
1 and 11.89 respectively. The thermodynamic
parameter, Gibbs free energy of solubilization (DG) was calculated
and found to be
29.63 kJ mol
1. The negative value of Gibbs free
energy of solubilization (DG) suggests that the solubilization of the
dye in saponin micelle was a likely and spontaneous process. The
micro structure of solubilized methyl violet in saponin micelles/
agglomerates shows that dye molecules were adsorbed on the
surface of agglomerated micelles (Fig. S1). Also, the particle size
distribution of saponin micelles and its agglomerates was
compared with the particle size distribution of methyl violet sol-
ubilized in saponin micelles/agglomerates (Fig. S2). The average
particle size of saponin micelles/agglomerates was 386 nm
whereas, average particle size of methyl violet solubilized saponin
micelles/agglomerates was measured as 540 nm. The enhancement
in particle size suggests that the dye molecules must have adsorbed
on the surface of agglomerates of saponin micelles. This increase in
the hydrodynamic size of methyl violet was due to the micellar
12 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16

Fig. 2. Variation in permeate ux and rejection of saponin and methyl violet in batch cell MEUF process: (a) with membrane MWCO; (b) with transmembrane pressure; (c) with pH;
(d) with NaCl salt concentration in feed (the concern parameter was varied and other parameter were Feed: 250 mg L
1 methyl violet and 2000 mg L
1 saponin, membrane MWCO:
10 kDa, transmembrane pressure drop: 200 kPa, pH: 6.5, Temperature: 27 3  C).

solubilization of saponin micelles in MEUF process.
The effect of solution pH on the micellar solubilization of methyl
violet was examined within the pH range of 3.0e12.5. Fig. 1(b)
shows the effect of solution pH on the solubilization of methyl vi-
olet. A slight increase in solubilization of methyl violet was
observed with increasing the pH up to pH 7 and beyond pH 7
solubilization started decreasing. The possible reason for this trend
is the competence of H ions to get adsorbed on the agglomerate of
saponin micelles as compared to the dye. The precipitates of methyl
violet were observed above pH 9 during the experiments which led
to lower solubilization of the dye.
The textile industry uses ionic salts at a high concentration with
the dyes. Therefore, the efuent coming out from such industry also
contains ionic salt. Therefore, the effect of NaCl concentration on
solubilization of methyl violet was evaluated at room temperature
(27 3  C). The effect of NaCl salt concentration on solubilization of
methyl violet is shown in Fig. 1(c). The solubilization capacity of
saponin micelles was observed to increase with increasing the NaCl
concentration in the surfactant solution. The presence of ionic salt
in saponin solution lowers the CMC of saponin surfactant and in-
crease the hydrophobicity which resulted in into enhanced solu-
bilization of dyes.
3.2. Micellar enhanced ultraltration in batch mode
The retention of the methyl violet and saponin by the mem-
branes having MWCO of 10, 20, 30, and 50 kDa is shown in Fig. 2 (a)
for a xed feed composition. The retention of dye by the MWCO 10
and 20 kDa membranes were >99% and >97% respectively, whereas
retention of 81% and 62% was achieved for MWCO 30 and 50 kDa
membrane respectively. However, the permeate ux was
maximum for the 50 kDa membrane among all the tested mem-
branes. The percentage retention of saponin by MWCO 10 kDa
membrane was maximum at 70.8%. On the basis of the % retention
of methyl violet as well as saponin and permeate ux, the 10 kDa
membrane was found adequate for the methyl violet and saponin
system. Therefore, MWCO 10 kDa was used for further experiments.
The effect of transmembrane pressure on the methyl violet and
saponin retentions was examined within the applied trans-
membrane pressure of 150e500 kPa. The permeate ux and the
solute retention is plotted against transmembrane pressure in Fig. 2
(b). It can be observed from the plot that the permeate ux was
increasing with increase in transmembrane pressure almost line-
arly because of the increase in effective driving force. However, the
dye and surfactant retention remained almost independent of
 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16
Fig. 3. Effect of feed composition in bath cell on permeate ux and rejection (methyl
violet in feed: 200 and 250 mg L
1, saponin in feed: 2000, 3000, 5000 and
10000 mg L
1, membrane MWCO: 10 kDa, transmembrane pressure: 200 kPa, tem-
perature: 27 3  C).
applied transmembrane pressure. This trend is an indication of
solubilization mechanism governed the retention of dye in the
MEUF process.
The variation of methyl violet and saponin retention with so-
lution pH is shown in Fig. 2 (c) at methyl violet concentration of
250 mg L
1, transmembrane pressure 200 kPa and saponin con-
centration of 2000 mg L
1. The retention of dye was independent of
solution pH which was because of the micellar solubilization as
well as the precipitation of dye at higher pH, although, the
permeate ux decreased with increase in pH. This decreasing trend
of ux was due to the concentration polarization which resulted in
the gel layer formation of precipitates on membrane surface
thereby increasing the pH.
The batch cell experiments were performed varying the NaCl
concentration from 0 to 50 g L
1 in the feed to examine the effect of
ionic salt in MEUF process for the dye removal. The concentration of
methyl violet and saponin in feed were xed at 250 mg L
1 and
2000 mg L
1 respectively. The experiments were carried out at a
transmembrane pressure of 250 kPa at room temperature
Fig. 4. Variation of permeate ux and rejection of methyl violet and saponin in cross ow cell (a) with cross ow rate (b) with transmembrane pressure drop (only the concern
parameter was varied and other parameter were, methyl violet concentration: 250 mg L
1, saponin concentration: 2000 mg L
1, membrane MWCO: 10 kDa, transmembrane
pressure: 200 kPa, cross ow rate: 0.8 LPM, temperature: 27 3  C).
13
(27 3  C), and the results are presented in Fig. 2 (d). The retention
of methyl violet remained higher than 99% with increasing salt
concentration. However, a slight increase in retention was observed
due to the reduced CMC of saponin in the presence of NaCl salt. The
retention of saponin was increased with increase in salt concen-
tration in the feed. The increasing saponin retention with an in-
crease in salt concentration suggests that the size of saponin
micelle might have grown in the presence of salt. Minor increase in
the permeate ux value was observed.
3.2.1. Effect of feed composition on permeate ux and rejection
To investigate the effect of methyl violet and saponin concen-
tration in the feed, the ratio of methyl violet concentration to
saponin concentration in the feed was varied from 200:0 to
200:10,000 mg L
1 and 250:0 to 250:10,000 mg L
1. All the ex-
periments were conducted at room temperature (27 3  C) with
operating transmembrane pressure of 200 kPa, and the results are
shown in Fig. 3. Higher than 99% methyl violet retention was ach-
ieved for all the feed composition having methyl violet concen-
tration of 200 and 250 mg L
1 in the feed. This trend suggests that
micellar solubilization mechanism and adsorption of methyl violet
on the agglomerates of saponin micelles could have responsible for
the higher retention of the dye. Also, it indicates that the methyl
violet has a strong afnity towards the saponin micelles and its
agglomerates. However, the maximum retention of saponin was
74% for feed methyl violet: saponin of 200:2000 mg L
1. With the
increase in saponin concentration decrease in saponin retention
and ux was observed. The permeate ux was higher for the mixed
feed of dye and surfactant as compare to only dye in the feed. The
membrane was cleaned manually with deionized water, and the
permeability was measured after each set of experiment. The same
membrane was used in successive experiments since no signicant
change in permeability was observed for a total operating time of
8 h. The surface morphology of fresh membrane and membrane
after 8 h of use in MEUF process were observed as shown in Fig. S3
(a) and Fig. S3 (b) respectively. The FE-SEM image shows some
difference in morphology of membrane surface which is because
some pore might have blocked during the MEUF process.
3.3. Micellar enhanced ultraltration in continuous mode
The change in methyl violet and saponin retention due to the
14 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16
Fig. 5. Effect of feed composition in cross-ow cell on permeate ux and rejection
(methyl violet in feed: 200 and 250 mg L
1, saponin in feed: 2000, 3000, 5000 and
10000 mg L
1, membrane MWCO: 10 kDa, transmembrane pressure: 200 kPa, tem-
perature: 27 3  C).
crossow rate was examined at a different cross ow rates. The
permeate ux and observed retention of methyl violet and saponin
at a cross ow rate of 0.5e1.2 LPM are presented as Fig. 4 (a). It was
found that the retention methyl violet and saponin remained
almost unchanged with increasing cross ow rate which indicates
the independence of the extent of micellar solubilization with cross
ow rate. The permeate ux increased marginally with increasing
cross ow rate due to the decreased gel layer resistance which gets
lowered at higher cross ow velocity.
Continuous cross ow experiments were performed to examine
the effect of transmembrane pressure drop on the methyl violet
Fig. 6. Recovery of saponin from aqueous solution (a) solvent and ARS solution (b) formation of emulsion after mixing (c) layer of the aqueous phase and solvent phase.
and saponin retentions. Fig. 4 (b) shows that the retentions of
methyl violet remained almost unchanged with increasing trans-
membrane pressure drop. This trend suggested that the retention
of the methyl violet was mainly due to the micellar solubilization
mechanism of the methyl on/into the saponin micelles. The varia-
tions of saponin retention with applied transmembrane pressure
which varied within a narrow range with an increase in trans-
membrane pressure drop. The change in permeate ux with
increasing the transmembrane pressure drop is shown in Fig. 4 (b)
within a transmembrane pressure range of 150e350 kPa. It was
observed that the permeate ux increased with increasing trans-
membrane pressure almost linearly. This trend was evident due to
enhancement in the driving force.
The effect of methyl violet to saponin concentration ratio in the
feed on the retention of methyl violet and permeate ux was tested
in continuous cross ow mode at room temperature (27 3  C).
The concentration ratio of methyl violet to saponin was varied by
changing the saponin concentration from 2000 to 10,000 mg L
1
and methyl violet concentration of 200 and 250 mgL
1. Fig. 5 shows
the permeate ux and retention of methyl violet and saponin for
various feed composition. With the increase in saponin concen-
tration decrease in permeate ux was observed. The reason for the
decline in permeate ux may be due to the increase in gel layer
formation of saponin agglomerates and micelles which added extra
resistance on membrane ltration. The retention of methyl violet
remained almost unchanged (>99%) for all the feed composition.
This trend indicated that saponin micelles solubilized all the dye
molecules. Comparison of batch mode and continuous cross-ow
mode conrmed that there was a noticeable improvement in ux
in continuous cross-ow mode; however, the retention remains
almost constant.
3.4. Recovery of saponin
The recovery of surfactant from the membrane stream is
 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16 15

Fig. 7. Effect of solvent to aqueous reetha solution ratio (v/v) on the recovery of
saponin.
necessary steps in any MEUF process from environmental as well as
economic point of view. Previously, Zhou et al. (2013) have tested
organobentonite for recovery of saponin from aqueous saponin
solution in phenanthrene contaminated soil washing (Zhou et al.,
2013). In another study, Mukhopadhyay et al. (2015) have applied
alkali treatment for As precipitation to recover saponin from As
contaminated saponin solution (Mukhopadhyay et al., 2015). Since
saponin is a nonionic surfactant, it is hard to recover saponin using
precipitation technique. Other potential methods for saponin re-
covery could be foam fractionation and liquid-liquid extraction
(Huang et al., 2017; Li et al., 2013). In the present study, two sol-
vents, n-butanol, and n-heptane were tested as a solvent for
saponin recovery in the solvent extraction process. The n-butanol
and n-heptane solution were mixed separately with fresh ARS so-
lution instead of mixing them directly with the permeate solution.
But the concentration of saponin in the solution was kept within
the limit of permeate saponin concentration. Also, the saponin
concentration in the solution was varied along with the solvent to
ARS ratio. When the solvent was added to the ARS solution (Fig. 6
(a)), it formed emulsion after mixing (Fig. 6 (b)). The mixed solu-
tion was kept unstirred and allowed to settle. The solvent and ARS
solution created two separate layers of aqueous phase and solvent
phase as shown in Fig. 6 (c). The aqueous phase separated out from
the solvent phase, and the saponin concentration in the aqueous
phase was measured by UV spectrometer. The percentage recovery
of saponin with a different volumetric ratio of solvent to aqueous
reetha solution (v/v) at various initial saponin concentrations is
shown in Fig. 7. It may be observed from the results that, when n-
butanol was used as a solvent, the surfactant recovery increased
from 40% to 85% with the increase in the solvent to ARS ratio from
1:5 to 1:1 at a xed saponin concentration of 350 mg L
1. The
similar trend was observed for higher initial saponin concentration
of 800, 2000, and 5000 mg L
1. This trend was due to the equilib-
rium distribution of saponin molecules in the solvent phase and
aqueous phase. However, the percentage recovery of saponin
decreased from 85% to 55% with the increase in initial saponin
concentration from 350 mg L
1 to 5000 mg L
1 at 1:1 solvent to
ARS ratio. This trend was apparent because the mass distribution of
saponin between solvent and aqueous phase was xed at a con-
stant temperature. The similar pattern of saponin extraction was
observed for the solvent n-heptane. However, the results suggested
that n-butanol was more effective solvent as compared to n-hep-
tane for the recovery of saponin. The recovered saponin can be
reused in MEUF process after separating it from the solvent. A
comparative study of some MEUF process reported in the literature
and present MEUF process is given in Table 2 along with the re-
covery method of surfactant. Since, saponin surfactant is a biode-
gradable natural surfactant and does not produce any secondary
pollution, therefore permeate containing saponin can be directly
utilized for the various cleaning purposes such as soil washing and
oor cleaning (Zhou et al., 2013; Mukhopadhyay et al., 2015).
4. Conclusion
This study demonstrated the micellar solubilization of methyl
violet dye in micelles of a biosurfactant saponin, followed by the
application of this biosurfactant in micellar enhanced ultraltration
(MEUF) process for the removal of methyl violet from wastewater.
The enhancement in solubilization of methyl violet in the presence
of saponin was mainly due to the micellar solubilization. Two
mechanisms were involved in micellar solubilization, i.e., incor-
poration of dye molecules inside the saponin micelles followed by
adsorption of dye molecules on the agglomerates of saponin mi-
celles. The micellar solubilization increased the hydrodynamic size
of the dye molecules which gave an advantage in MEUF process.
The percentage removal of methyl violet was more than 99% at
different studied conditions. Saponin from the permeate stream
was recovered successfully using two solvents, n-butanol, and n-
heptane. The biosurfactant which is biodegradable and eco-friendly

Table 2
Comparison of the present MEUF process and surfactant recovery method with literature.

Surfactant Pollutant DP Surfactant in feed Pollutant in Pollutant Surfactant Surfactant Surfactant Reference
(kPa) feed retention retention recovery method recovery

CPC Eosin dye 276 10,000 mg L
1 10 mg L
1 70.45% 97.40% Chemical 99.78% Purkait et al., 2004
precipitation
SDS and CPC Cu 2 and potassium 345 25,000 mg L
1 and 3500 mg L
1 91% and 92% and Chemical 86.75% and Das et al., 2008
permanganate 10,000 mg L
1 and 100 97% 96.5% precipitation 80.6%
SDS and TritonX-100 Cd2 70 860 mg L
1 and 50 mg L
1 >85% 30% e e Hui Huang et al.,
140 mg L
1 2009
SDS and OMC-10 Methylene blue 200 4  8.3  10
3 and 0.5 mg L
1 91.36% 80% e e Bielska and
5.4  10
4 mol L
1 Szymanowski,
2006
SDS and LAS Cd2, Cu2, Ni2, 100 9 mmol L
1 and 10 mg L
1 >90% e e e Samper et al., 2009
Pb2, and Zn2 4 mmol L
1 except
Ni2
Saponin Methyl violet 200 2000 mg L
1 250 mg L
1 >99% >71% Solvent extraction >82% Present study
(n-Butanol)
16 K. Samal et al. / Journal of Environmental Management 203 (2017) 8e16

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