Colloids and Surfaces A: Physicochem. Eng.

Aspects 425 (2013) 122128

Contents lists available at SciVerse ScienceDirect
Colloids and Surfaces A: Physicochemical and
Engineering Aspects
j our nal homepage: www. el sevi er . com/ l ocat e/ col sur f a
Enhanced soil washing of phenanthrene by a plant-derived natural
biosurfactant, Sapindus saponin
Wenjun Zhou
a,b,
, Xuehao Wang
a
, Cuiping Chen
a
, Lizhong Zhu
a,b
a
Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China
b
Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou, Zhejiang 310058, China
h i g h l i g h t s

Enhancing soil washing of a natu-

ral biosurfactant of Sapindus saponin
was studied.

Sapindus saponin showed great

washing capability for phenanthrene
contaminated soil.

Sorption of Sapindus saponin on soil

was much less than synthetic surfac-
tants.

Sapindus saponin solution can be

recovered after soil washing.
g r a p h i c a l a b s t r a c t
The washing efciencies of Sapindus saponin for phenanthrene contaminated soil were only slightly less
than those of Tween 80, and Sapindus saponin solutions can be recovered for their reusage after soil
washing by using organo-bentonite to remove phenanthrene from the washed surfactant solutions with
an appropriate dosage.
a r t i c l e i n f o
Article history:
Received 8 November 2012
Received in revised form17 February 2013
Accepted 28 February 2013
Available online 6 March 2013
Keywords:
Biosurfactant
Sapindus saponin
Soil washing
Phenanthrene
pH
Recovery
a b s t r a c t
Biosurfactants have great advantages for using in environmental remediation as their environmental
friendly nature. In this study, a plant-derived natural biosurfactant of Sapindus saponin was extracted
fromthe fruit pericarps of Sapindus mukorossi (Chinese soapberry), and the properties of this biosurfactant
inenhancing washing for phenanthrene contaminated soil were investigated and compared with those of
Tween80, a representative synthetic nonionic surfactant. Sapindus saponin showed a linear solubilization
enhancement for phenanthrene and the weight solubilization ratio was 0.0312 and about one third of
that of Tween 80. However, Sapindus saponin can effectively remove phenanthrene from contaminated
soil with a maximum removal percentage of about 87.4%, which was only slightly less than that of Tween
80 (about 91.5%) because the sorption of Sapindus saponin onto soil was much less than that of Tween
80. The solubilization enhancement of Sapindus saponin for phenanthrne and the sorption of Sapindus
saponin onto soil both decreased with increasing solution pH, the net results of which resulted in that the
maximumwashing efciency of Sapindus saponin for phenanthrene contaminated soil was obtained at
pH around 6.0. Sapindus saponin solutions can be recovered for their reusage after soil washing by using
organo-bentonite to remove phenanthrene from the washed surfactant solutions with an appropriate
dosage. Sapindus saponin showed a favorable performance in enhancing soil washing and should have
the potential application in soil washing technology for the remediation of organic contaminated soils
and groundwater.
2013 Elsevier B.V. All rights reserved.

Corresponding author at: Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China. Tel.: +86 571 88982591;
fax: +86 571 88982591.
E-mail address: [email protected] (W. Zhou).
0927-7757/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.02.055
W. Zhou et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 425 (2013) 122128 123
1. Introduction
Thecontaminationof soils andgroundwater bytoxic and/or haz-
ardous organic pollutants is a widespread environmental problem.
The removal of hydrophobic organic compounds (HOCs) fromcon-
taminated soils or groundwater is becoming a major concern as
their water-insoluble characteristics may retain those compounds
in solid phase and then pose a long-termthreat to ecological safety
and human health [1]. Surfactant enhanced soil washing has been
suggested as one of the promising technologies for the remediation
of HOCs-contaminated soils and groundwater in recent years [2,3].
Afewstudies for the practical application of surfactants in in situ or
ex situ soil washing indicated the potential of using surfactants to
cleanupthe residual andsorbedHOCs fromthe eld-contaminated
soils and subsurface environments [1].
Enhanced soil washing generally has been performed with syn-
thetic surfactants, including anionic, nonionic, cationic and mixed
surfactants, and some of them have shown great washing capa-
bilities for HOCs from contaminated soils and groundwater [1].
However, the residual synthetic surfactants in soils and ground-
water have the potential toxicity risk or hazard to environment
and human health. So, an improved strategy for soil washing tech-
nology is to use the surfactants with low environmental impact.
Recently, biosurfactants caused increasing interest in soil washing
technology because they generally exhibited greater environmen-
tal compatibility, lower toxicity, and higher biodegradability in
comparing with synthetic surfactants [47].
Biosurfactants are natural compounds and found in animals,
plants and microbes. Some studies have shown that biosurfactants
can also effectively enhance the removal and/or biodegradation of
HOCs in contaminated soils [5,6]. Therefore, biosurfactants seemto
be better candidates for using insoil washing technology. However,
literature data indicated that most of previous studies have focused
on microbial biosurfactants produced by yeast or bacteria, includ-
ing rhamnolipids, surfactin, sophorolipids and so on [46]. More
other biosurfactants should be investigated for their properties in
enhancing soil washing because they may have more promising
properties, e.g., the plant-derived biosurfactants.
Saponins are a class of natural biosurfactants and widely dis-
tributed in plant kingdom [8]. Some natural saponins have been
traditionally used as detergent for fabric washing, hair and body
cleaning and in folk medicine. A few studies have shown that
saponins can effectively remove heavy metal or crud oil from
contaminated soils [6,911] and also showed great solubilization
capability for PAHs [7]. So, saponins have the potential capability
in enhancing HOCs removal fromcontaminated soils and ground-
water.
Saponins existing in diverse plant species generally showgreat
difference in their structure and properties [8]. However, almost
all of previous studies for saponins in environment application
focused on Quillaja saponin obtained fromthe bark extracts of the
South American tree Quillaja Saponaria [57,911] because there
exists only a few plants providing a larger source of saponins,
hence are worth extracting for commercial use. Sapindus mukorossi
Gaerth (Chinese soapberry) is a saponin-rich plant with its fruits
and widely distributed in China and other tropical and subtropical
regions of Asia [1214]. The fruit pericarp of S. mukorossi contains
of up to 10% by weight of Sapindus saponin that makes it to be one
of the strongest commercial sources for saponin. Sapindus saponin
has wide application currently as additives in medicines, cleansers,
beverages, confectionery and cosmetics [8,15]. However, few sci-
entic researches have reported the environment application of
Sapindus saponin.
In this study, the plant-derived natural biosurfactant of Sapin-
dus saponin was extracted from the fruit pericarp of S. mukorossi,
and the properties of this biosurfactant in enhancing solubilization
and soil washing for phenanthrene were investigated, meanwhile
the corresponding effect of pH was evaluated and the recovery
of Sapindus saponin solutions after soil washing was tested. The
specic objectives of this study are to investigate and evaluate
the performance of Sapindus saponin in enhancing washing for
phenanthrene-contaminated soils and then provide valuable infor-
mation for the application of Sapindus saponin in soil washing
technology for the remediation of HOCs-contaminated soils and
groundwater.
2. Materials and methods
2.1. Materials
Dry fruits of S. mukorossi were gathered from Hangzhou city,
China. The outer fruit pericarps were dried in an oven at 50

C
for about 2 days and then ground and sieved through a standard
sieve of 60 meshes, which was used as raw materials for the
extraction of Sapindus saponin. Phenanthrene was selected as a
representative polycyclic aromatic hydrocarbon (PAH) to model
HOCs and obtained fromAcros Organics (USA) with a purity of 99%.
Tween 80 was obtained fromAcros Organics (USA) as a representa-
tive synthetic nonionic surfactant. Hederagenin was obtained from
Tauto Biotech Co. (China) with a purity >98% and used to deter-
mine sapogenincontent inthe extractedSapindus saponin. Selected
physicochemical properties for these chemicals were presented in
Table 1. All other chemicals used were of reagent grade quality and
higher.
A natural bentonite (Na
+
-montmorillonite) was collected from
Inner Mongoliaof Chinafor thesorptionexperiments of surfactants,
of which the organic carbon content, specic surface area (BET-
N
2
) and cation exchange capacity (CEC) are 0.04%, 60.9m
2
/g and
105mequiv/100g, respectively. Organo-bentonitewas preparedby
modifyingthe natural bentonite witha cationic surfactant (hexade-
cyltrimethylammoniumbromide, HDTMAB) at 1.0 times CEC with
the methods as described by Zhu et al. [18], which was used to test
the recovery of Sapindus saponin solution after soil washing.
A clean natural soil was collected from Hangzhou city, China,
which was air-dried and sieved to obtain particles less than 1mm
for the preparation of phenanthrene contaminated soil. The soil
contains 5.9% sand, 67.5% silt and 26.6% clay, which was analyzed
withLaser Particle Size Analyzer (MalvernMAM-5005, UK). The soil
organic carbon content was determined to be 1.54%, and the pH of
soil solution was measured to be 6.5. Phenanthrene contaminated
soil was prepared with the methods described by Zhou and Zhu
[19], and the prepared contaminated soil was aged for about two
weeks before the experiments, which had a nal concentration of
178mg/kg for phenanthrene and was used directly in the batch
experiments.
2.2. Extraction of Sapindus saponin
Sapindus saponin was extracted and puried with the methods
as described by Ma et al. [14]. Briey, the fruit pericarp power of S.
mukorossi was extracted two times with 75% ethanol by ultrasoni-
cation for 30min at a solid/liquid ratio of 1:6 (w/v). After ltration
and evaporation, the extract was redissolved in distilled water
and then owed through a column lled with macroporous resin
(D101). After that, the column was eluted sequentially with dis-
tilled water, 30% ethanol and 70% ethanol in the volume of three
times the breakthrough volume (BV). The eluent from70% ethanol
was collected and evaporated to dryness, and the resulting prod-
uct was the extracted Sapindus saponin. The solid of extract was
directly dissolved in distilled water to prepare Sapindus saponin
124 W. Zhou et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 425 (2013) 122128
Table 1
Selected physicochemical properties of compounds in this study
a
Compounds Molecular formula MW logKow Sw (mg/L) CMC (mg/L)
Phenanthrene C
14
H
10
178.23 4.57 1.18 -
Tween 80 C
8
H
17
C
6
H
4
O(OCH
2
CH
2
)
9.5
H 1310 40
Hederagenin C
30
H
48
O
4
472.7
a
Phenanthrene data fromYaws [16] and Tween 80 data fromZhu and Zhou [17].
solutions, and the concentrations of themwere expressed with the
mass of solid extract in unit volume of solution.
Sapogenin content in the extracted Sapindus saponin was mea-
sured with the methods described by Li and Li [20] and used to
express the purity of the extracted Sapindus saponin. pH of Sapin-
dus saponin solution was determined in the varying concentration
from0.1g/L to1.0g/L. Surface tensionof Sapindus saponinsolutions
over a wide concentration range were determined with a Model 20
surface tensionmeter (Fisher Scientic, USA). Critical micelle con-
centration (CMC) of Sapindus saponin solution was obtained with
the methods as described by Zhou et al. [7].
2.3. Surfactant sorption experiments
Bentonite was used to evaluate the sorption of Sapindus saponin
onto soil incomparing withthat of Tween80. Batchsorptionexper-
iments were conducted in triplicate with the methods as described
by Zhu and Zhou [17]. Briey, 0.5g of bentonite was mixed with
20mL of surfactant solutions in 22mL Corex centrifuge tube with
Teon-lined screw caps. After shaking (24h, 201

C) and subse-
quently centrifugation (30min, 3000rpm), an appropriate aliquot
of the supernatant was withdrawn and analyzed for surfactants.
The sorption amount of surfactants onto bentonite was computed
simply fromthe difference of the initial and nal concentrations of
surfactants in solution.
2.4. Solubiliation enhancement experiments
Batch experiments were conducted in duplicate to measure
the solubility enhancement of phenanthrene by Sapindus saponin
and Tween 80. 20mL of surfactant solutions with a series of con-
centrations were placed in 22mL Corex centrifuge tubes, and
solid phenanthrene was subsequently added to each tube in
amount slightly more than required to saturate the solution. After
shaking (24h, 201

C) and subsequently centrifugation (30min,

3000rpm), an appropriate aliquot of the supernatant was then
carefully withdrawn with a volumetric pipette and the aqueous
concentrations of phenanthrene were analyzed by HPLC, the mean
values of which were used to plot solubilization curves.
2.5. Soil washing experiments
Enhanced washing of surfactant solutions for phenanthrene
fromcontaminated soil was conducted triply in batch experiment.
2.0g of contaminated soil was weighed into 22mL Corex centrifuge
tube, to which 20mL of surfactant solutions with different concen-
trations were added. All aqueous solutions for soil tests contained
0.01M NaCl to keep a constant ionic strength and 0.01% (w/w)
NaN
3
to inhibit microbial growth. After shaking (24h, 201

C)
and subsequently centrifugation (30min, 3000rpm), an appro-
priate aliquot of the supernatant was removed and analyzed for
phenanthrene by HPLC. The losses of phenanthrene by photochem-
ical decomposition, volatilization and biodegradation were found
to be negligible during the experiment process. The removal ef-
ciencies of phenanthrene by surfactant solutions were calculated
in according to the equilibriumconcentrations of phenanthrene in
aqueous solutionandits initial concentrationoncontaminatedsoil.
2.6. Recovery of Sapindus saponin solution after soil washing
The recovery of Sapindus saponin solution was tested in batch
experiments withaninitial surfactant concentrationof 10g/L. After
the rst soil washing experiments, organo-bentonite was added
into the washed Sapindus saponin solutions at the dosages of 1g/L,
2g/L and 5g/L, respectively, which was shaken for 6h at 201

C
and then centrifugated at 5000rpm for 30min. After determin-
ing phenanthrene concentrationinaqueous solution, the recovered
Sapindus saponinsolutions were reusedfor soil washingwithabove
experiment process.
2.7. Analytical methods
In surfactant sorption experiments, the aqueous concentrations
of Sapindus saponin and Tween 80 were quantied by UV spec-
trophotometer (Shimadzu UV-2401PC, Japan) at the wavelengths
of 210 and 234nm, respectively. All phenanthrene concentra-
tions in aqueous solutions were quantied by a Agilent 1100
HPLC (USA) tted with UV detector and Eclipse XDB-C18 column
(4.6mm150mm, 5m) using methanol-water (v/v, 90/10) as the
mobile phase at a ow rate of 1mL/min. The UV wavelength for
phenanthrene was set at 250nm.
3. Results and discussion
3.1. Structure and properties of Sapindus saponin
Saponins are a structurally diverse class of compounds in many
natural plants, which are characterized by a skeleton derived of
the 30-carbon precursor oxidosqualene to which glycosyl residues
are attached. Traditionally, they are subdivided into steroidal and
triterpene glycosides, which consist of nonpolar aglycones coupled
with one or more monosaccharide moieties [8]. The combination
of polar and non-polar structural elements in saponin molecules
explains their surface-activities in aqueous solutions.
Sapindus saponin extracted from the fruit pericarp of S. muko-
rossi contains some complex components with different structure,
and then it is fairly difcult to accurately dene the structure and
composition of this natural biosurfactant. Recently, several com-
ponents for Sapindus saponin were isolated and characterized in
some studies [15,21]. Among them, the most common structure
reported is the oleanane-type triterpenoid saponin that consists of
a hederagenin as the aglycones, which is substituted with a di- or
trisaccharide at C-3 (Fig. 1). These characterized components for
Sapindus saponin have the varied molecular weight from 604 to
966 with the corresponding molecular formula of C
35
H
56
O
8
and
C
50
H
78
O
18
[21].
In this study, a yield of about 23.3% (m/m) was obtained for
the extracted Sapindus saponin, which still was a complex mixture
containing Sapindus saponin, glycosides, and other sugars. Gen-
erally, sapogenin content can be used to express saponins purity
[20]. With Fig. 1, hederagenin is the sapogenin of Sapindus saponin,
and its content in the extracted Sapindus saponin was determined
to be about 14.4%. With the characterized structure for Sapindus
saponin in Fig. 1, hederagenin content should be about 48.978.3%
in the pure component of Sapindus saponin. So, it can be inferred
W. Zhou et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 425 (2013) 122128 125
Fig. 1. Main structures of Sapindus saponins extracted from the fruit pericarps of
Sapindus mukorossi Garetn [15,21].
that Sapindus saponin content in the extract of this study is about
18.429.4%.
The extracted Sapindus saponin in this study was characterized
by determining pH, surface tension, CMC and elemental composi-
tion. The pH of Sapindus saponin solution varied from5.8 to 5.0 as
the concentration increased from 0.1g/L to 10.0g/L and then did
not vary beyond 1%. The acidic nature of Sapindus saponin solu-
tion can be due to the acidic and ionizable functional groups in the
hydrophilic fraction of Sapindus saponin molecules. The CMC value
of Sapindus saponin solution was determined to be about 120mg/L,
which is similar to that of some commercial nonionic surfactant.
With surfactant concentration above CMC, a stable value of about
32mN/mwas obtained for surface tension, which is similar to the
range of 3040mN/mreported for several commercial surfactants.
According the elemental analysis, the element percentage compo-
sitions of the extracted Sapindus saponin were 55.4% for carbon,
37.1% for oxygen and 7.5% for hydrogen.
3.2. Sorption comparison of surfactants onto soil
Sorption of surfactants onto soil would decrease the effective
concentrations of surfactant inaqueous solutiontosolubilize HOCs,
and the soil-sorbed surfactants can also enhance soil retardation
capability for HOCs, both of which would reduce soil washing ef-
ciency and result in an increase in remediation times and costs.
Thus, a quantitative evaluation for any potential surfactant wash-
ing approach must consider the sorption of surfactant onto soils to
maximize efciency and minimize remediation costs.
As the disturbance of soil organic matter, it is fairly difcult to
accurately quantify the total concentrations of Sapindus saponin
in aqueous solution by UV spectrophotometer after soil sorption
experiments. So, anatural clayof bentonitewithloworganic carbon
content was used to investigate the sorption of Sapindus saponin in
this study, which was compared with that of Tween 80. The sorp-
tion of Sapindus saponin and Tween 80 onto bentonite was shown
in Fig. 2 as a function of surfactant equilibrium concentration.
Both sorption isotherms are nonlinear with typical S-shape curves,
but they show different variation tendency with increasing sur-
factant concentrations. The sorption isotherm of Tween 80 shows
a sharp increase and then reaches a plateau at equilibrium con-
centration around the CMC, but a gradual increase is observed for
the sorption amounts of Sapindus saponin with increasing equilib-
riumconcentration and the sorption plateau could not be observed
in the studied concentrations even though equilibriumconcentra-
tions aboveCMC. Theexperimental datafor thesorptionof Sapindus
saponin were tted to the Langmuir isothermequation
q
e
=
q
m
K
L
C
e
1 +K
L
C
e
(1)
Fig. 2. Comparison of the sorption of Sapindus saponins and Tween 80 onto ben-
tonite.
where q
m
is the maximumsorption amount (g/kg); K
L
is the model
constant; C
e
is the equilibrium concentration of sorbate in aque-
ous solution (g/L). The model results were shown in Fig. 2, which
indicated that Langmuir isothermmodel can describe the sorption
of Sapindus saponin well, supported by the high correlation coef-
cient (R
2
>0.995) and the good agreement of experimental data
with simulated curve.
With Fig. 2, the sorption amounts of Tween 80 onto bentonite
are obviously higher than those of Sapindus saponin. With a given
initial concentration of 10g/L, about 44% Tween 80 was adsorbed
onto bentonite, but the sorption loss of Sapindus saponin was only
about 8%. So, the sorption of Sapindus saponin onto soil is much
less than that of Tween 80. The sorption of surfactants onto soils
is generally attributed to the hydrogen bonding and electrostatic
attraction between the negatively charged soil surface and the sur-
factant molecules. With Fig. 1, Sapindus saponin molecules contain
ionizable carboxyl groups and then some species with negative
charge exist in surfactant solutions, which can enhance the elec-
trostatic repulsion between Sapindus saponin molecules and the
negatively charged soil surface and then restrain the sorption of
Sapindus saponin molecules onto soils.
3.3. Solubilization enhancement of phenanthrene by Sapindus
saponin
Enhanced solubilization for HOCs is always used as an index
in evaluating the capabilities of surfactants in soil washing. Sol-
ubilization enhancement of phenanthrene by Sapindus saponin
solutions was measured, and the apparent solubilities (S

w
) of
phenanthrene in aqueous solution were shown in Fig. 3 as a func-
tion of Sapindus saponin concentrations. Obviously, the S

w
values
for phenanthrene have a linear increase with increasing Sapin-
dus saponin concentrations above the CMC (the linear equations
were listed in Fig. 3), which is consistent with a micellar solubili-
zation mechanism[2224]. The enhancement extent of surfactants
for HOCs solubilization generally can be evaluated by the ratio of
S

w
/S
w
, where S
w
is the water solubility of HOCs. The correspond-
ing S

w
/S
w
values for phenanthrene in Sapindus saponin solutions
were also showninFig. 3, withwhichSapindus saponinshows great
capability in enhancing phenanthrene solubilization. For example,
the S

w
values of phenanthrene in 3000mg/L of Sapindus saponin
solutions is about 26.5 times of its S
w
values. The enhanced solu-
bilization of Tween 80 for phenanthrene was also shown in Fig. 3,
whichis obviously great thanthat of Sapindus saponin. Witha given
126 W. Zhou et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 425 (2013) 122128
0 500 1000 1500 2000 2500 3000 3500
0
20
40
60
80
100
120
y = 0.0113x + 0.6209
R = 0.9988
S
w
*

f
o
r

P
h
e
n
a
n
t
h
r
e
n
e

(
m
g
/
L
)
Surfactant concenrtrations (mg/L)
Tween 80
Sapindus saponin
y = 0.0312x + 0.9775
R = 0.9996
0
20
40
60
80
100
S
w
*
/
S
w

f
o
r

P
h
e
n
a
n
t
h
r
e
n
e
Fig. 3. Solubilization enhancement of phenanthrene by Sapindus saponins and
Tween 80.
surfactant concentration of 3000mg/L, the S

w
value of phenan-
threne in Tween 80 solution is about three times of that in Sapindus
saponin solution.
A common expression in quantifying the solubilization capacity
of surfactants for HOCs is known as the weight solubilization ratio
(WSR) [22], the mass of solubilized HOCs by the unit mass of sur-
factant in solution above its CMC. In the presence of excess solutes,
WSR value can be obtained fromthe slope of solubilization curve,
in which solute concentrations are plotted against surfactant con-
centrations above CMC. The WSR values of Sapindus saponin and
Tween 80 for phenanthrene were obtained fromthe slope of solu-
bilizationcurves inFig. 3andtheresults werelistedinTable2. Some
reported WSR values of representative synthetic surfactants for
phenanthrene were also listed in Table 2 to compare and evaluate
the solubilization capability of Sapindus saponin for phenanthrene.
The WSR value of Sapindus saponinfor phenanthrene is about 1/3to
1/2 of those of the selected synthetic surfactants, and thenthe solu-
bilization capability of Sapindus saponin for phenanthrene is much
less than these synthetic surfactants, which can be contributed to
the low purity of Sapindus saponin in the extract. To reach higher
soilubilization capability for phenanthrene, new extract method
shouldbedevelopedtoextract Sapindus saponinwithhigher purity.
3.4. Enhanced soil washing by Sapindus saponin solutions
Enhanced washing of Sapindus saponin solutions for phenan-
threne contaminated soil was conducted with batch equilibrium
experiments, and the washing efciencies were expressed with
the removal percentages of phenanthrene fromcontaminated soil,
which were shown in Fig. 4 as a function of Sapindus saponin
Table 2
Comparison of the solubilization enhancement of Sapindus saponins for phenan-
threne with some representative synthetic nonionic surfactants.
Surfactants MW WSR Ref.
Sapindus saponins 0.0113 This study
Tween 80 1310 0.0312 This study
0.033 Li and Chen [22]
0.0258 Prak and Pritchard [23]
Tween 20 1228 0.0203 Prak and Pritchard [23]
0.021 Li and Chen [22]
TX-100 625 0.034 Li and Chen [22]
0.0316 Edwards et al. [24]
Brij 58 1124 0.0285 Prak and Pritchard [23]
Brij 35 1198 0.0193 Prak and Pritchard [23]
0 5 10 15 20 25 30
0
20
40
60
80
100
R
e
m
o
v
e
d

p
h
e
n
a
n
t
h
r
e
n
e

(
%
)
Surfactant concentration (g/L)
Tween 80
Sapindus saponins
Fig. 4. Soil washing efciency of phenanthrene by Sapindus saponins and Tween 80.
concentrations. The removal percentages of phenanthrene from
the contaminated soil by Sapindus saponin solutions show a
sharp increase at low surfactant concentration and then smoothly
increase to reach the stable maximum values of about 87.4%. So,
Sapindus saponin can effectively enhance phenanthrene removal
fromcontaminated soils.
The removal percentages of phenanthrene by Tween 80 were
also shown in Fig. 4, which are obviously higher than those of
Sapindus saponin at a given surfactant concentration, but they did
not show the expected multiple in according with the solubili-
zation capability of Tween 80 for phenanthrene. The WSR value of
Tween 80 for phenanthrene is about three times of that of Sapindus
saponin, but the removal efciencies of Tween80for phenanthrene
are only slightly great than those of Sapindus saponin. For example,
with a certain surfactant concentration of 10g/L, the removal per-
centages of phenanthrene by Tween 80 and Sapindus saponin are
about 87.2% and 78.1%, respectively. This result could be attributed
to the weak sorption of Sapindus saponin onto soils. The sorption
of surfactants onto soils would result in the decrease of surfactant
concentrations in aqueous solution and the partition of HOCs into
the immobile sorbed surfactant, which would reduce the washing
efciencies of surfactants for HOCs contaminated soil [25,26]. It
can be inferred that Sapindus saponin with higher purity may show
greater soil washing capability than Tween 80.
3.5. Effect of pH on the soil washing of Sapindus saponin
Effects of pH on phenanthrene solubilization and soil washing
by Sapindus saponin solution were studied at various pH between
4.0 and 9.0, which was adjusted with buffer solutions at the same
concentration of 0.01M. The WSR values of Sapindus saponin for
phenanthrene at different solution pHwere obtained fromthe cor-
responding solubilization curves (data not shown) and the results
were shown in Fig. 5, which showa gradual decrease with increas-
ing pH from 4.0 to 6.0 and then a sharp decrease at pH above
6.0. The WSR value at pH 9.0 is only about 1/5 of that at pH 4.0.
So, the solubilization capability of Sapindus saponin for phenan-
threne has strong dependence on solution pHand the lowsolution
pH is favorable for Sapindus saponin in enhancing phenanthrene
solubilization, which can be attributed to the effect of pH on the
species of Sapindus saponin molecule in solution. With increased
pH, more Sapindus saponin molecules were ionized and then the
net charge on the head groups of Sapindus saponin molecules
increased, which caused the electrostatic repulsion between
the head groups of Sapindus saponin molecules. The increasing
W. Zhou et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 425 (2013) 122128 127
4 5 6 7 8 9
0.000
0.004
0.008
0.012
0.016
0.020
R
e
m
o
v
e
d

p
h
e
n
a
n
t
h
r
e
n
e

(
%
)
W
S
R

f
o
r

p
h
e
n
a
n
t
h
r
e
n
e
pH
WSR
0
20
40
60
80
100
Removal percentages
Fig. 5. Effect of pH on the solubilization enhancement and soil washing of Sapindus
saponin for phenanthrene.
electrostatic repulsion between Sapindus saponin molecules can
inuence the micelle aggregation and then decrease the hydropho-
bicity of saponin micelle, which would reduce the partition of
phenanthrene into saponin micelles and then the solubilization
capability of Sapindus saponin for phenanthrene [7].
Effect of pH on the washing efciencies of Sapindus saponin for
phenanthrene contaminated soils was measured at a xed sur-
factant concentration of 10g/L, and the corresponding removal
percentages of phenanthrene were also shown in Fig. 5, with which
the removal percentages of phenanthrene have a slight increase
with increasing pH from 4.0 to 6.0 and then a sharp decrease at
pH above 6.0. The removal percentage of phenanthrene by Sapin-
dus saponin at pH 9.0 is about 1/2 of that at pH 6.0. However, the
washing efciencies of Sapindus saponin for phenanthrene did not
show the same tendency as the solubilization capabilities of it for
phenanthrene with varied solution pH.
With Fig. 5, the WSR values of Sapindus saponin for phenan-
threne gradually decrease with increasing pH from4.0 to 6.0, but a
slight increase is observed for the removal percentages of phenan-
threne, whichcouldbe attributedto the effect of pHonthe sorption
of Sapindus saponin onto soils. The increasing pH can promote the
ionization of the acidic groups in Sapindus saponin molecules and
thenenhance the electrostatic repulsionbetweenSapindus saponin
molecules and the negatively charged soil surface, with which the
sorption of Sapindus saponin onto soils decreased with the increas-
ing pH. At pH 6.0, the solubilization capability of Sapindus saponin
for phenanthrene was less than that at pH 4.0, but the sorption of
Sapindus saponinontosoil at pH6.0was alsoless thanthat at pH4.0,
the net results of whichresultedinthat that the maximumwashing
efciencies of Sapindus saponin solutions for phenanthrene con-
taminated soils was observed at pH around 6.0.
3.6. Recovery and reusage of Sapindus saponin solution
In the in situ and ex situ washing for HOCs contaminated
soils, the recovery and reusage of surfactant solution after soil
washing are necessary for saving the cost, for which HOCs need
to be removed from the washed surfactant solutions. Organic-
bentonite was tested to remove phenanthrene from the washed
Sapindus saponin solutions with an original surfactant concentra-
tion of 10g/L. After the rst soil washing, the removal percentage
of phenanthrene from contaminated soil was about 78.1% and
phenanthrene concentration in the washed Sapindus saponin solu-
tions was about 13.9mg/L.
Fig. 6 shows the removal of phenanthrene from the washed
Sapindus saponin solutions by organo-bentonite and the
1 g/L 2 g/L 5 g/L
0
20
40
60
80
100
R
e
m
o
v
e
d

p
h
e
n
a
n
t
h
r
e
n
e

(
%
)
organo-bentonite dosage
From the washed Sapindus saponin solutions
Second washing from contaminated soil
Fig. 6. Removal of phenanthrene from the washed Sapindus saponin solutions by
organo-bentoniteandthesubsequent washingefciencies of therecoveredSapindus
saponins solutions for phenanthrene contaminated soil.
subsequent washing efciencies of the recovered Sapindus saponin
solutions for phenanthrene contaminated soil. The removal per-
centages of phenanthrene from the washed Sapindus saponin
solutions increase from about 58.5 to 91% with the increasing
dosages of organo-bentonite from 1.0g/L to 5.0g/L. So, organic-
bentonite can effectively remove phenanthrene from the washed
surfactant solutions. A same tendency can also be observed
for the second washing efciencies of the recovered Sapindus
saponin solutions for phenanthrene contaminated soil, which
increase fromabout 45.6% to 65.5% with the increasing dosages of
organo-bentonite in recovering Sapindus saponin solutions. So, the
second soil washing efciencies of the recovered Sapindus saponin
solutions depended on the removal of phenanthrene from the
washed surfactant solutions.
The removals of phenanthrene from surfactant solutions by
organo-bentonite depend on the distribution of phenanthrene
between surfactant micelles in aqueous solution and the cationic
surfactant in organo-bentonite. Based on available literature [27],
the cationic surfactant in organo-bentonite is more effective parti-
tion mediumfor HOCs than surfactant micelle in aqueous solution.
So, organo-bentonite can be used as the effective sorbent in remov-
ing HOCs fromthe washedsurfactant solutions for the recovery and
reusage of Sapindus saponin solutions after soil washing.
4. Conclusions
This study investigated the enhanced soil washing of a plant-
derivednatural biosurfactant of Sapindus saponinfor phenanthrene
from contaminated soil. Sapindus saponin can effectively remove
phenanthrene from contaminated soil with a maximum removal
percentage of about 87.4%, which was only slightly less than that of
Tween 80 because the sorption of Sapindus saponin onto soil was
much less than that of Tween 80. The low solution pH is favorable
for Sapindus saponin in enhancing phenanthrene solubilization,
and the maximum washing efciency for phenanthrene contam-
inated soil was obtained at pHaround 6.0. The recovery of Sapindus
saponin solutions can be attained by using organo-bentonite to
remove phenanthrene fromthe washedSapindus saponinsolutions
after soil washing. With the results of this study, Sapindus saponin
showed a favorable performance in enhancing soil washing and
should have potential application in soil washing technology for
the remediation of organic contaminated soils and groundwater.
128 W. Zhou et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 425 (2013) 122128
Acknowledgments
This study was nancially supported by Zhejiang Provincial
Natural Science Foundation of China (LZ12B07001), National Natu-
ral Science Foundation of China (21137003), the Key Innovation
Team for Science and Technology of Zhejaing Province, China
(2009R50047), and the Fundamental Research Founds for the Cen-
tral Universities (2012FZA6010).
References
[1] S. Paria, Surfactant-enhanced remediation of organic contaminated soil and
water, Adv. Colloid Interface Sci. 138 (2008) 2458.
[2] J.H. Harwell, D.A. Sabatini, R.C. Knox, Surfactants for grounder water remedia-
tion, Colloid Surf. A: Physicochem. Eng. Asp. 151 (1999) 255268.
[3] C.N. Mulligan, R.N. Yong, B.F. Gibbs, Surfactant-enhanced remediation of con-
taminated soil: a review, Eng. Geol. 60 (2001) 371380.
[4] N. Christo, I.B. Ivshina, A review: microbial surfactants and their use in eld
studies of soil remediation, J. Appl. Microbiol. 93 (2002) 915929.
[5] C.N. Mulligan, Environmental applications for biosurfactants, Environ. Pollut.
133 (2005) 183198.
[6] C.N. Mulligan, Recent advances in the environmental applications of biosurfac-
tants, Curr. Opin. Colloid Interface Sci. 14 (2009) 372378.
[7] W.J. Zhou, J.J. Yang, L.Z. Zhu, Solubilization properties of polycyclic aromatic
hydrocarbons by saponin, a plant-derived biosurfactant, Environ. Pollut. 159
(2011) 11981204.
[8] J.-P. Vincken, L. Heng, A. Groot, H. Gruppen, Saponins, classica-
tion and occurence in the plant kingdom, Phytochemistry 68 (2007)
275297.
[9] K.-J. Hong, S. Tokunaga, T. Kajiuchi, Evaluation of remediation process with
plant-derived biosurfactant for recovery of heavy metals from contaminated
soils, Chemosphere 49 (2002) 379387.
[10] K. Urum, T. Pekdemir, Evaluation of biosurfactants for crude oil contaminated
soil washing, Chemosphere 57 (2004) 11391150.
[11] W.-J. Chen, L.-C. Hsiao, K.-Y. Chen, Metal desorption fromcopper(II)/nickel(II)-
spiked kaolin as a soil component using plant-derived saponic biosurfactant,
Proc. Biochem. 43 (2008) 488498.
[12] K. Nakayama, H. Fujino, R. Kasai, Y. Mitoma, N. Yata, O. Tanaka, Solubilizing
properties of saponins fromSapindus mukorossi Gaertn, Chem. Pharm. Bull. 34
(1986) 32793283.
[13] Y. Fu, P. Lei, Y. Han, D. Yan, Investigation on the process of Sapindus saponin
puried with macroporous adsorption resin and screening of its bacteriosta, J.
Chin. Med. Mater. 33 (2010) 267272.
[14] Y.-B. Ma, Y.-X. He, L.-X. Peng, J.-W. Wu, Z.-J. Mi, Study on isolation and purica-
tion of Saponin fromSapindaceae with macroporous resin, Chin. J. Exp. Tradit.
Med. Formulae 17 (2011) 2325.
[15] H.C. Huang, M.D. Wu, W.J. Tsai, S.C. Liao, C.C. Liaw, L.C. Hsu, Y.C. Wu, Y.H.
Kuo, Triterpenoid saponins from the fruits and galls of Sapondus mukorossi,
Phytochemistry 69 (2008) 6091616.
[16] C.L. Yaws, Chemical Properties Handbook, McGraw-Hill, Beijing, 1999.
[17] L.Z. Zhu, W.J. Zhou, Partitioning of polycyclic aromatic hydrocarbons to solid-
sorbed nonionic surfactants, Environ. Pollut. 152 (2008) 130137.
[18] L.Z. Zhu, Y.M. Li, J.Y. Zhang, Sorption of organobentonites to some organic pol-
lutants in water, Environ. Sci. Technol. 31 (1997) 14071410.
[19] W.J. Zhou, L.Z. Zhu, Efciency of surfactant enhanced desorption depending on
the component characteristics of soil-PAHs-surfactant system, Environ. Pollut.
147 (2007) 6673.
[20] H. Li, P. Li, HPLC-ELSD determination of hederagenin and oleanolic acid in Flos
Lonicerae, Chin. J. Pharm. Anal. 26 (2006) 820822 (in Chinese).
[21] H.C. Huang, S.H. Liao, F.R. Cheang, Y.H. Kuo, Y.C. Wu, Molluscicidal saponins
from Sapindus mukorossi, inhibitory agents of Golden Apple Snails, Pomacea
canaliculata, J. Agric. Food Chem. 51 (2003) 49164919.
[22] J.-L. Li, B.-H. Chen, Solubilization of model polycyclic aromatic hydrocarbons
by nonionic surfactants, Chem. Eng. Sci. 57 (2002) 28252835.
[23] D.J.L. Prak, P.H. Pritchard, Solubilization of polycyclic aromatic hydrocarbon
mixtures in micellar nonionic surfactant solutions, Water Res. 36 (2002)
34633472.
[24] D.A. Edwards, R.G. Luithy, Z. Liu, Solubilizationof polycyclic aromatic hydrocar-
bons in micellar nonionic surfactant solutions, Environ. Sci. Technol. 25 (1991)
127133.
[25] S. Paria, K.C. Khilar, A review on experimental studies of surfactant sorption
at the hydrophilic solidwater interface, Adv. Colloid Interface Sci. 110 (2004)
7595.
[26] W.J. Zhou, L.Z. Zhu, Inuence of surfactant sorption on the removal of phenan-
threne fromcontaminated soils, Environ. Pollut. 152 (2008) 99105.
[27] L.Z. Zhu, B.L. Chen, S. Tao, C.T. Chiou, Interactions of organic contaminants with
mineral-adsorbed surfactants, Environ. Sci. Technol. 37 (2003) 40014006.