RSC Advances

View Article Online

PAPER View Journal | View Issue
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.

Switchable anionic surfactants for the remediation

of oil-contaminated sand by soil washing†
Cite this: RSC Adv., 2014, 4, 4638
Elize Ceschia, Jitendra R. Harjani, Chen Liang, Zahra Ghoshouni, Tamer Andrea,
R. Stephen Brown* and Philip G. Jessop*

Received 17th September 2013
Accepted 2nd December 2013
DOI: 10.1039/c3ra47158f
www.rsc.org/advances
Soil remediation requires technologies to restore contaminated soil to a state that is environmentally acceptable.
In most cases, while the soil can be remediated the contaminant itself cannot be reclaimed. However, ex situ soil
washing with an aqueous solution of a surfactant would allow easy recovery of the contaminant if the resulting
emulsion could be easily and reliably broken. CO2-responsive switchable surfactants that can be switched on
and off by CO2 addition and removal would allow facile emulsion breaking, but all reported examples are
cationic surfactants. Because soil washing requires anionic surfactants, we have investigated phenolate,
benzoate and carboxylate salts as switchable anionic surfactants. These surfactants can indeed be switched
on and off with CO2. Three switchable anionic surfactants (sodium 2-nitro-4-((octyloxy)carbonyl)phenolate
(1a), sodium 4-(octyloxy) benzoate (3a) and sodium laurate (4a)) and two commercial nonswitchable
surfactants (sodium dodecyl sulfate (SDS) and Triton X-100) were evaluated for their ability to wash Ottawa
Sand artificially contaminated with North Sea crude oil. At 50
C, all three switchable surfactants were able to
remove North Sea crude oil from sand and have the added feature of facile oil separation and recovery from
the wash mixture after CO2 treatment.

In soil washing, surfactants are used to liberate the oil from

1 Introduction
Ex situ soil washing is one of the most versatile contaminated soil
remediation techniques because it can be applied to virtually all
target organic contaminants: e.g. petroleum hydrocarbons,
metals, PCBs, pesticides and PAHs.1 The goals of soil washing are
to remove the contaminant from the soil and to concentrate the
contaminants for further treatment.2 Normally, the soil is rst
screened and divided into two fractions: sand and nes (silt and
clay). Sand, the subject of the present study, is the major
component and is easier to treat because of the larger particle
size and lower organic matter content.3 Aer size separation, any
volatile contaminants present in the fractions are removed by
heating the soil. Soil washing is usually performed with hot
aqueous solutions of surfactants because higher temperatures
help to reduce the viscosity of contaminants like oil4 and increase
the solubilizing ability of the surfactants, although the higher
temperature increases energy costs. The cleaned soil is then
removed and the wash water is treated and recycled. Oil-con-
taining sludge, contaminated nes, and contaminated water are
sent to wastewater treatment facilities.
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ON, K7L 3N6,
Canada. E-mail: jessop@chem.queensu.ca; Fax: +1 (613) 533-6669; Tel: +1 (613) 533-
3212
† Electronic supplementary information (ESI) available: Experimental methods,
synthesis and characterization of compounds 1b and 2b, characterization and
properties of the North Sea crude oil, emulsion stability tests, oil content of
sand before and aer weathering. See DOI: 10.1039/c3ra47158f
the soil in part by reducing the interfacial tension between the
oil and the water, as well as decreasing the attraction between
the contaminant and the soil. However, surfactants tend to
continue to stabilize an emulsion of the contaminant oil in
water long aer the washing is performed, making it difficult to
separate the oil from the water. Switchable surfactants, which
can switch off upon command, could facilitate both the
washing and then the subsequent oil/water separation.
Switchable surfactants have surface activity that can be
switched “on” or “off” upon application of a trigger such as
light,5 pH6,7 or redox reagents.8–16 The switchable cationic
surfactants developed by Jessop and co-workers are pH
switchable and designed specically to respond to pH changes
induced by the introduction and removal of CO2 from solu-
tion.17,18 To date, these switchable surfactants have been found
to have the ability to stabilize oil/water emulsions,17,18 and to
have potential utility in emulsion polymerization19,20 and the
transport of very heavy crude oils through pipelines.21
Switchable surfactants triggered by CO2 seemed ideal for a
process for soil washing because they could facilitate oil and
surfactant recovery, but the reported examples of such
surfactants are all cationic. Cationic surfactants do not
perform well in soil washing because they bind to anionic sites
in the solid material.22 Not surprisingly, switchable cationic
surfactants are also ineffective for soil washing. We therefore
needed to nd CO2-triggered switchable anionic surfactants
(SAS).

4638 | RSC Adv., 2014, 4, 4638–4645 This journal is © The Royal Society of Chemistry 2014
 View Article Online

Paper RSC Advances

Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.

Scheme 1 Anionic surfactants tested for their response to CO2

Fig. 1Proposed scheme for soil washing using switchable surfactants. addition and removal. In each case, “a” refers to the sodium salt
For simplicity, stages such as soil screening, washing of oversize (sodium phenolate or carboxylate) and “b” refers to the acid form
material, and separation of fines from the water are not shown. (phenol or carboxylic acid).

2 Results and discussion

A SAS would be expected to function as an emulsion-stabi- 2.1 CO2-Triggered switchable anionic surfactants
lizing surfactant in the absence of CO2, while the SAS is in its
In our study of potential switchable anionic surfactants, we
anionic form (A in eqn (1)). Addition of CO2 would convert it
evaluated two phenolate sodium salts, one benzoate and one
into its neutral form (HA), which should not be able to stabilize
carboxylate (Scheme 1).
emulsions. Removal of CO2 should reverse the reaction. One
Switching the sodium phenolate surfactants (1a, 2a) off with
would expect this transformation to be possible provided that
CO2 and on again by removal of CO2 was tested by visual
the addition of CO2 lowers the pH well below the midpoint of
observation, 1H NMR spectroscopy, pH monitoring, and surface
the acid HA (i.e. the pH at which 50% of the SAS in the system is
tension measurements. Clear yellow solutions of 1a were
in the neutral form) and the removal of the CO2 restores the pH
prepared in situ by dissolving 1b (5 mM) and NaOH (7.5 mM) in
to a value well above the midpoint.
H2O (for the NMR experiments, D2O and 8 equivalents of
CO2 ;H2 O
Naþ A ) * HA þ Naþ HCO (1) Na2CO3 were used instead). The use of excess NaOH produced a
3
pH of 11.4. Aer CO2 was introduced into the vial, the pH
Literature reports support the expectation that sodium dropped to 5.6 (Table 1), phenol 1b precipitated, and the solu-
carboxylate salts should be reversibly switchable. It has been tion almost completely decolorized within 5 min (Fig. S1†), due
known for many years that exposure of aqueous solutions of
fatty acid sodium salts to CO2 causes the air/water surface
tension to change.23 Moore and Lefevre24 described an emul- Table 1 pH of SAS solutions during several switching cycles, where a
cycle consists of a CO2 treatment followed by a heat treatment
sion polymerization using sodium oleate as the surfactant and
styrene and acrylonitrile as the comonomers. Aer the latex 1a [A]0 2b [A]0 3b [A]0 4c [A]0
was produced, they showed that it could be destabilized by the Treatment ¼ 5 mM ¼ 5 mM ¼ 5 mM ¼ 5 mM
addition of CO2, presumably because the acid form of the
surfactant was less effective than the anionic form at latex None 11.4 11.7 11.2 8.4
CO2 5.6 5.8 5.8 5.6
stabilization. The use of pressurized CO2 to lower the pH
1 cycle 8.2 9.5 8.6 8.2
below 3.7, in order to break emulsions containing anionic 1 cycle + CO2 5.6 5.8 5.9 5.8
surfactants, has also been described.25 Therefore, sodium 2 cycles 8.5 9.2 8.6 7.8
oleate and related anionic surfactants appear to be switchable 2 cycles + CO2 5.7 5.8 6.0 5.7
anionic surfactants. However, useful SAS would ideally require 3 cycles 8.3 9.0 8.4 8.1
3 cycles + CO2 5.8 5.9 5.9 5.6
neither pressurized CO2 nor pH values as low as 3.7 to be
4 cycles 8.5 9.3 8.6 8.4
switched off. 4 cycles + CO2 5.8 5.8 5.9 6.1
We propose that SAS could be used to facilitate the oil/water 5 cycles 8.7 9.1 8.4 8.9
separation stage in the soil washing process, as shown in pKa of acid 5.4d 5.3e 4.5f 5.3 (ref. 26)
Fig. 1. Aer the washing is completed and the soil has been a
pH of a solution of 1b (5 mM) and NaOH (7.5 mM) in H2O treated to
separated, the washing solution would be brought into a alternating treatments of CO2 bubbling for 10 min followed by heating
separator. CO2 would be introduced, causing the surfactant to to 70
C for 1 h. b pH of a solution of 2b (5 mM) or 3b (5 mM) and NaOH
(7.5 mM) in H2O treated to alternating treatments of CO2 bubbling for
be “turned off” and resulting in the separation of the crude oil 10 min followed by heating to 70
C for 3 h. c pH of 5 mM sodium
and surfactant from the wash water. The crude can then be laurate (4a) solutions in H2O treated to alternating treatments of CO2
reclaimed and recycled, while the wash water would be bubbling for 10 min followed by heating to 60
C for 1 h. d pKa for the
analogous ethyl ester.27 e pKa for the analogous methyl ester, this
decarbonated, recombined with the surfactant, and re-intro- work. f pKa for the analogous 4-butoxybenzoic acid.28
duced into the washer.

This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 4638–4645 | 4639

RSC Advances
to the poor solubility of the neutral phenol 1b. 1H NMR spec-
troscopy of the liquid phase showed that there was no longer
any detectable quantity of either 1a or 1b in solution. Heating
the mixture to 70
C for 1 h to remove most of the CO2 raised the
pH to 8.2, re-dissolved the precipitate and restored the yellow
colour to the solution. NMR spectroscopy conrmed that the
amount of dissolved 1a had returned to the original amount.
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.
Repeated cycles gave the same results, showing that the
behaviour is fully and repeatedly reversible. This reversible
change was also evident in the air/water surface tension of the
aqueous solution, which was 57–63 dynes cm2 in the presence
of CO2 and 33–35 dynes cm2 in the absence of CO2. Similar
switching behaviour was observed with a solution of 2.
Introduction of CO2 into aqueous solutions of sodium
carboxylate surfactants (3a, 4a) converts the carboxylate anion
into the poorly soluble carboxylic acid; a 5 mM solution of
sodium dodecanoate (4a) had a pH of 8.4, but aer CO2 was
bubbled through the solution for 10 min the pH dropped to 5.6
and dodecanoic acid precipitated as a white powder (Table 1). In
order to switch the surfactant back to the anionic form, the
solution was heated to 60
C for 1 h, causing the CO2 to dissi-
pate and the acid to redissolve as the pH rose to 8.2. Note that
the switching of compounds 1a–4a from anionic form to the
acid form occurs even though the pH never drops below the pKa
of the acid form (see Section 2.2 for an explanation).
Peters29 and Wakelin30 reported that the interfacial tension
between benzene and aqueous glycine buffer solutions, in the
presence of decanoic acid (58 mM relative to water content), is
roughly constant at 30 dynes cm1 (cf. 35 with benzene/water
alone) at pH values below 7 but drops dramatically if the pH is
raised to 8 or 9; the value at pH 8.2 is 24 dynes cm1. Decanoate
is much more effective than decanoic acid at lowering the
benzene/water interfacial tension. This justies referring to the
acid form of alkanoic acids as “switched off” surfactants relative
to the sodium alkanoate salts.
We found that emulsions of 1-octanol and water, stabilized
with sodium dodecanoate, were stable for hours if prepared
under air but separated immediately if prepared in a CO2-
saturated environment (Fig. S3†). The phenolate surfactants,
like the carboxylates, are capable of stabilizing 1-octanol/water
emulsions in the absence of CO2 but not in its presence
(Fig. S2†).
2.2 The pH values required for switching SAS
Switching of an anionic surfactant A between its anionic form
and its neutral form (eqn (3)) requires using CO2 to adjust the
pH back and forth between two values, one above and one below
the midpoint. For these purposes, the midpoint is dened as
the pH at which half of the surfactant in the system (not merely
that in the aqueous phase) has been protonated to the neutral
form HA. We can predict the pH of the midpoint, and therefore
the pH values required for switching, by using a simple math-
ematical model of the solubility and reaction equilibria.
Considering an aqueous solution of A, at an initial
concentration of [A]0 and in the absence of an oil phase, the
pH required to “switch off” an anionic surfactant A (eqn (3))
4640 | RSC Adv., 2014, 4, 4638–4645
View Article Online
Paper
depends on the pKa of the neutral form HA, the solubility of HA,
and the initial concentration of A (i.e. [A]0). In the unlikely
situation that both A and HA are completely soluble at all
relevant concentrations, then the % protonation of A is only
dependent on the pH and the pKa (eqn 2 and 3) and the
midpoint occurs when the pH matches the pKa. In this scenario,
the CO2 treatment would have to reduce the pH to a value
signicantly below the pKa in order to effectively switch off the
surfactant. Penth25 recommended a pH of 3.3 in order to break
emulsions stabilized by carboxylate surfactants. In our experi-
ments, we did not achieve a pH that low and yet we were still
able to switch off the surfactant.
A(aq) + H3O+(aq) # HA(aq) + H2O(l) 1/Ka,HA (2)
!
½A 0  ½A  ½H3 Oþ 
% protonation ¼ ¼ (3)
½A 0 ½H3 Oþ  þ Ka
If the neutral form of the carboxylic acid has a solubility limit
below 0.5[A]0, then the pH of the midpoint will be shied to a
value higher than the pKa. This is oen the case for carboxylate
soaps because the critical micelle concentration (CMC) of NaA
(23–28 mM for sodium dodecanoate)31,32 is usually much higher
than the solubility limit for the neutral acid. Thus the switching
of the anionic surfactants can be achieved by using CO2 to
adjust the pH between two values that straddle the midpoint
and that are both well above the pKa.
The pH-dependent solubility and the pH-dependence of the %
protonation can be modelled mathematically by assuming that
the sodium salt NaA is soluble at all relevant concentrations
while HA has an intrinsic solubility limit S0. While S0 is
pH-independent, the observed solubility S (the solubility of HA
and A combined) is pH-dependent and follows the Henderson–
Hasselbalch equation (eqn (4)).33 The intrinsic solubility of
protonated surfactants is rarely published, but it can be esti-
mated from the observed solubility of the acid in pure water
(Saq, eqn (5)).34 This method is not particularly accurate because it
relies on a single data point, but it usefully generates an
approximate value of S0. Fortunately, the S0 of dodecanoic acid
was reported by Nyren and Back to be 2.3  105 M.26 The
pH-dependent solubility, calculated using eqn (5), is shown for
dodecanoate/dodecanoic acid in Fig. 2; this graph is identical to
the one reported by Nyren and Back. As the pH is lowered by the
addition of acid or CO2, the pH at which the surfactant solubility
drops dramatically is well above the pKa.
S ¼ S0 (1 + Ka/[H3O+]) (4)
!
Ka
Saq ¼ S0 1 þ (5)
ðS0 Ka þ Kw Þ1=2
The pH dependence of the % protonation of A is governed
by eqn (4) for conditions in which [HA] < S0 and by eqn (6) for
conditions in which [HA] ¼ S0. This calculates the % proton-
ation for all of the A/HA in the system, not just that in the
aqueous phase. A plot of the % protonation (Fig. 2) shows that
the limited solubility of HA dramatically increases the pH of the
midpoint. Thus the pH of the midpoint is greater than the pKa
This journal is © The Royal Society of Chemistry 2014
 View Article Online

Paper RSC Advances

2.3 Washing oil-contaminated sand with switchable and

nonswitchable surfactants
We compared three SAS (compounds 1a, 3a, and 4a) with two
non-switchable surfactants (Scheme 2): an alkylsulfate (sodium
dodecylsulfate (SDS)) and a neutral surfactant (Triton X-100).
SDS is a fairly ubiquitous anionic surfactant used in a variety of
products, and has been reported as a common reference
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.

surfactant.35 Triton X-100 is a non-ionic, biodegradable surfac-

Fig. 2 The pH-dependent solubility of dodecanoic acid (solid line) in
water calculated using eqn (4) and an S0 value of 2.3  105 M. Also
shown is the pH dependence of the % protonation of a 5 mM (nominal
concentration) dodecanoate solution calculated using eqn (3) and (6)
assuming that dodecanoic acid in its neutral form has (a) infinite
solubility (dotted line) or (b) a solubility limit of 2.3  105 M (dashed
line). The midpoints are at pH 5.3 and 7.3, respectively.
for an anionic surfactant if [A]0 > 2S0. For dodecanoic acid, the
pH of the midpoint is 8.3, 7.3, or 6.6 for initial concentrations
([A]0) of 50 mM, 5 mM, and 1 mM, respectively. Our results
(Table 1) show that for a 5 mM solution of sodium dodecanoate,
the pH of the solutions in the presence and absence of CO2 are
5.8 and 8.3, which is consistent with the predicted midpoint
of approximately 7.3. Hence it is not necessary for the pH to
drop below the pKa in order to convert an anionic surfactant to
the neutral form; a drop below the solubility-modied midpoint
is sufficient.
 
½A 0  ½A  Ka S0
% protonation ¼ ¼1 (6)
½A 0 ½H3 Oþ  þ ½A 0
Scheme 2 The two surfactants used in this study that are non-
switchable (not CO2-responsive).
tant that is one of the family of alkylphenol “polyethoxylates”
(RC6H4(OC2H4)xOH) which have been reported in the soil
washing literature.2,36 The benzoate surfactant 3a was chosen to
determine whether an aromatic ring would make the surfactant
more effective compared to aliphatic carboxylates in terms of
solubilization of oil. Because the purpose of our initial experi-
ments was neither to optimize the process nor to determine the
best surfactant, but rather to demonstrate whether switchable
surfactants are capable of soil washing, we tested only a single
concentration of surfactant; 1 wt% was chosen because it is
above the CMC for all the surfactants studied (Table 2).
Samples of oil-contaminated soil were prepared articially.
To simplify this initial study, Ottawa Sand was chosen as a
model “soil” matrix for the washing studies. Ottawa Sand is a
nonporous silica sand which contains little organic matter and
has a particle size range of typically 0.1 to 1.0 mm.43,44 Our
sample had a particle size range of 0.5 to 1.5 mm, measured by
optical spectroscopy. Future work will need to evaluate the
effect of different sands and soils on the process performance.
The sand was articially contaminated with a light crude, North
Sea crude oil (properties given in Table S1†).
The contaminated sand was weathered for these studies.
Weathering is an important process in the articial contami-
nation of the sand because it better mimics real environmental
samples. In real soil washing applications, the soil has been
weathered by exposure to ambient conditions for an extended
time, which increases the binding of the contaminants to the
soil matrix and makes remediation more difficult.35
Various batches of contaminated and articially-weathered
sand were created for this work (Table S2†), containing 2.6 to 3.1
wt% oil aer the weathering. The average percent mass of oil
lost during weathering was 26%.
Soil washing experiments were done at room temperature
(23
C) and at elevated temperature (50
C). The room temper-
ature experiments were intended to determine the surfactants'
performance without the aid of heating, which should maxi-
mize the difference in washing performance between

Table 2 Surfactants (non-switchable and switchable) studied for sand washing

Surfactant MW (g mol1) Solubility (g L1) CMC (mM) CMC (g L1) CMC wt%

SDS 288.4 150 (ref. 37) 8.0 (ref. 38) 2.3 0.23
Triton X-100 625 Soluble39,40 0.24 (ref. 39) 0.15 0.015
1a 318.1 N/A 2.8a 0.89 0.089
3a 272.3 N/A 14a 3.8 0.38
4a 222.3 12 (ref. 41) 24 (ref. 42) 5.3 0.53
a
Determined experimentally. See ESI.

This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 4638–4645 | 4641

RSC Advances
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.
Fig. 3 The sand washing process at room temperature.
surfactants. Furthermore if the switchable surfactants per-
formed well at room temperature, it would increase the desir-
ability of these chemicals because their usage could potentially
reduce the energy cost of soil washing. Elevated temperatures
increased the efficiency of soil washing, as expected, because
solubility and desorption kinetics are increased, and the
viscosity of the oil is reduced which helps to solubilize the oil.4,35
Contaminated and weathered sand samples (5 g) were
washed with 10 g solutions of surfactant (Fig. 3). Typically, two
or three distinct layers are apparent aer washing: (1) sand on
the bottom, (2) an opaque, tan coloured aqueous layer, and (3)
in some cases, a thin oil layer was observed on the top. All
surfactants removed at least some oil from the sand during the
washing. In contrast, water without surfactant was unable to
remove a signicant amount of oil. Of the ve surfactants, 1a
visually appeared to remove the most oil from the sand
(Fig. S5†).
Aer the washing was completed, the liquid phase of the
wash mixture was decanted into a separate vial (rst decant).
The sand was then rinsed with 50 mL of deionized water. The oil
contents of the washed sand, the decanted surfactant solution,
and the rinse solution were all determined.
The amount of oil remaining on the sand aer washing was
determined by organic solvent extraction of the residual oil
using a 1 : 1 v:v mixture of dichloromethane and hexanes. At
room temperature, the switchable surfactant 1a and the non-
switchable surfactant Triton X-100 were reasonably effective
Fig. 4 Comparison of the average% removal of oil from sand by the
surfactants after sand washings at room temperature (white) and 50
C
(grey). Error bars represent the standard deviation (n ¼ 3).
4642 | RSC Adv., 2014, 4, 4638–4645
View Article Online
Paper
(Fig. 4). For all surfactants, the oil removal from the sand was
visibly more complete and faster at 50
C than at room
temperature, as expected. At 50
C, all of the switchable and
non-switchable surfactants were reasonably effective.
2.4 Processing of the decanted wash mixture
The purpose of using a switchable surfactant is to facilitate the
recovery of the contaminant and the surfactant. In typical soil
washing operations using conventional surfactants, the wash
mixture (emulsied oil in water) is generally sent for further
treatment, including by aeration, ltration, adsorption using
activated carbon, reverse osmosis and electrodialysis.45,46 These
treatments will recover the water, but the surfactant and
contaminant are non-recoverable due to biodegradation or
subsequent treatments, along with the difficulty of separating
them. Both the contaminant and the surfactant are potentially
valuable components and, if recovered and re-used, waste could
be reduced and revenue generated to offset the cost of reme-
diation. When a switchable surfactant is turned off it may
destabilize (break) the emulsion.
Emulsions stabilized by cationic or anionic surfactants can
be broken by increasing the ionic strength by addition of a salt.
While this process is effective and fairly simple, there are
drawbacks, including the cost of purchasing the salt and
treating and disposing of the salty aqueous waste. We found
that the SDS wash solution emulsions could be broken by
adding NaCl until a distinct oil/water phase separation was
observed. The samples were le to settle overnight, but sepa-
ration began almost immediately aer salt addition. Regardless
of whether the washing had been performed at room temper-
ature or 50
C, separation by salt addition was achieved; there
was no oil visually evident in the clear and colourless water
layer, and the mixture could not be re-emulsied by shaking or
stirring. However, the salt addition also caused the SDS to
precipitate, and the oil adhered to the solid surfactant particles
to make a tan-coloured slurry layer above the water. Salt addi-
tion did not cause the separation of the wash solutions con-
taining Triton X-100.
Even without addition of salt, the wash solution emulsions
partially settled out. Some of the oil creamed to form a thin layer
above the bulk emulsion. If le overnight, the amount of oil in
the aqueous phase dropped by 70% for both SDS and Triton X-
100. When CO2 was bubbled through the emulsion immediately
aer washing, the amount of creaming was the same, and the
amount of oil remaining in the aqueous phase also dropped by
70%. This demonstrated that CO2 does not help break the wash
solution emulsions when non-switchable surfactants are used.
In all cases, this separation by creaming is not permanent; even
a mild disturbance of the vials caused the creamed oil to re-
enter the emulsion.
The wash solution emulsions containing switchable surfac-
tants were effectively broken by the addition of CO2. The
reduction in pH caused the precipitation of the surfactant in its
neutral form, causing the mixture to become visibly turbid.
Aer 10 min of bubbling CO2, precipitation of the surfactant
was complete; foaming ceased and the components (oil, water
This journal is © The Royal Society of Chemistry 2014
 View Article Online

Paper RSC Advances

Table 3 Evaluation of the Removal of Oil from the Bulk Aqueous

Phase after Washing at Room Temperaturea

goil/Laq before goil/Laq aer % Removal of oil

Surfactant Treatment treatment treatment from aq. phase

SDS NaCl 1.7 0.35 79

X-100 NaCl or CO2 5.8 — None
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.

1a CO2 2.6 0.48 81

3a CO2 2.2 1.0 55
4a CO2 1.4 0.63 55
a
% Removal ¼ {1  (oil mass aer CO2)/(oil mass before CO2)}  100%.

Table 4 Evaluation of the Removal of Oil from the Bulk Aqueous

Phase after Washing at 50
Ca
Fig. 5 Average percent oil in various compartments after the washing
of contaminated sand using surfactant 1a at 50
C.
goil/Laq before goil/Laq aer % Removal of oil
Surfactant Treatment treatment treatment from aq. phase
separate from the rinse to maximize the efficiency of further
SDS NaCl 9.8 0.25 98
X-100 NaCl or CO2 11 — None
recovery. Of the 78% of the oil in the wash mixture, 73% was
1a CO2 4.4 0.32 93 isolated in an oil layer aer the surfactant was switched off, with
3a CO2 6.7 0.73 89 the other 5% remaining in the wash water. The potential for
4a CO2 11 0.5 95 recovering a signicant portion of the oil removed from the
a
% Removal ¼ {1  (oil mass aer CO2)/(oil mass before CO2)}  100%. sand has been demonstrated, though the recovered oil may
need further treatment before it can be used.
Further work is needed to determine the fate of the surfac-
tant throughout the wash process. The residual surfactant on
and surfactant) no longer formed an emulsion. Separation of the cleaned sand was about 0.45%, while the amount in the
the phases did not occur, however, as rapidly as it did in wash water, aer precipitation of the 1b form, was 0.48%. We
samples with SDS treated with NaCl. The treated wash mixtures were not able to separate effectively the precipitated 1b from 1b
were le to stand overnight, during which time the separation dissolved in the oil layer due to the small scale of our experi-
of the crude oil and surfactant from water occurred (Tables 3 ments. A larger scale operation with specialized handling
and 4). While CO2 treatment was always done at room equipment would be able to recover and then reuse some of the
temperature, the quality of the separation was better if the surfactant, though recovery from the wash oil layer will require
washing step had been performed at 50
C than at room development of additional separation procedures.
temperature. Particularly with 1a and 4a, the oil contamination
remaining in the aqueous phase was nearly as low aer the CO2
and settling treatment as it was with SDS aer NaCl treatment. Conclusions
The switchable surfactants allowed the oil to be separated much
Carboxylate and phenolate anionic surfactants can be deacti-
more effectively than neutral Triton X-100, though slightly less
vated and precipitated by the addition of an atmosphere of CO2,
effectively than SDS. The switchable surfactants used the
which lowers the pH below the midpoint of the surfactant (the
benign and easily removed trigger CO2, so that the water would
pH corresponding to 50% protonation). The pH required to
not require expensive desalination before reuse.
destabilize emulsions is not as low as the pKa; the limited
solubility of the neutral form of the surfactant causes the
2.5 Fate of the oil and surfactant midpoint to move to signicantly higher pH values.
The overall performance of the soil washing for the optimal The switchable surfactants presented are able to remove
case, using surfactant 1a at 50
C, is summarized by tracking the crude oil from contaminated sand and afford subsequent
average amount of the oil in the various compartments as separation of the crude oil from the water upon CO2 treatment.
shown in Fig. 5. The initial wash mixture contained 78% of the At room temperature, switchable surfactant 1a and non-
oil originally on the sand aer careful decanting. Another 13% switchable surfactant Triton X-100 had reasonable oil-
of the oil was removed with the water rinse step, indicating that removable performance, while at 50
C all of the switchable
closer to 90% could likely be removed in the initial wash with a surfactants and Triton X-100 removed at least 90% of the oil
more efficient separation method. The nal “cleaned” sand had from contaminated sand, while non-switchable surfactant SDS
3% of the initial oil remaining (i.e. the contamination of the performed nearly as well.
sand by oil decreased from 30 000 mg kg1 before washing to Aer washings at 50
C with switchable surfactants, treat-
800 mg kg1 aerwards). The initial wash mixture was kept ment of the wash solutions with CO2 gas triggered the

This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 4638–4645 | 4643

RSC Advances
precipitation of the surfactant and the breaking of the emul-
sion, lowering the concentration of oil in the water by up to 95%
and lowering the concentration of surfactant in the water by up
to 99.5% relative to the original concentration.
In contrast, washing the sand with aqueous solutions of the
non-switchable surfactant SDS removed less oil from the sand
and gave emulsions that could not be broken by CO2 addition,
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.
although salt addition did break the emulsions. Washing the
sand with aqueous solutions of the non-switchable surfactant
Triton X-100 gave emulsions that could not be broken by either
CO2 or salt addition.
Experimental methods
Experimental methods are described in the ESI.† The procedure
for the washing of oil-contaminated sand is also shown here for
the convenience of the reader.
All sand washings were done in triplicate. Approximately 5.0 g
of the contaminated sand, 10 g of the desired surfactant solution,
and a stir bar were placed into a 20 mL vial, which was then capped
with a poly(tetrauoroethylene)-lined lid. The samples were
shaken by hand for 20 s, placed in an otherwise empty 150 mL
beaker (for support) and then stirred at 470 rpm for 1 h, re-shaken
for another 20 s and stirred for another hour. For the washings at
50
C, the samples were placed directly into the water bath, which
was previously heated to 50
C. Aer the 2 h, the samples were le
to stand briey to let the solution settle. Fig. S4† illustrates the
sand washing process and Fig. S5† shows photographs of some of
the samples at the start and end of the 2 h washing period.
Aer the washing was completed, the liquid phase of the
wash mixture was decanted into a separate 20 mL vial and the
mass was recorded. This initial decanted solution will be
referred to as the rst decant. The sand was then rinsed with 50
mL of deionized water and the rinses were combined in a 100
mL Wheaton jar and are referred to as the rinse solution. The
rinse solution was analyzed for oil content as described in
section 1.7.3 of the ESI.†
A small sample of the decant solution was removed for
analysis (see section 1.7.2 of the ESI†). The vial containing the
remainder of the decant was capped with a rubber septum. CO2
was bubbled into the vial using a syringe needle at a ow rate of
3 to 5 mL min1 for 10 min. A separate syringe needle was used
as a vent. Aer 10 min, the vial was re-capped with a lid and le
to settle overnight, aer which the aqueous phase was again
analyzed for oil content.
Acknowledgements
The authors gratefully thank the Natural Sciences and Engi-
neering Research Council of Canada and Albonia Innovative
Technologies for funding. PGJ also acknowledges support from
the Canada Research Chairs Program.
Notes and references
1 L. K. Wang, in Site remediation and groundwater
decontamination, CRC Press, 2007.
4644 | RSC Adv., 2014, 4, 4638–4645
View Article Online
Paper
2 S. Deshpande, B. J. Shiau, D. Wade, D. A. Sabatini and
J. H. Harwell, Water Res., 1999, 33, 351–360.
3 M. J. Mann, J. Hazard. Mater., 1999, 66, 119–136.
4 M. I. Kuhlman and T. M. Greeneld, J. Hazard. Mater., 1999,
66, 31–45.
5 H. Sakai, A. Matsumura, S. Yokoyama, T. Saji and M. Abe, J.
Phys. Chem. B, 1999, 103, 10737–10740.
6 A. F. Dexter, A. S. Malcolm and A. P. J. Middelberg, Nat.
Mater., 2006, 5, 502–506.
7 C. B. Minkenberg, L. Florusse, R. Eelkema, G. J. M. Koper
and J. H. v. Esch, J. Am. Chem. Soc., 2009, 131, 11274–11275.
8 T. Saji, K. Hoshino and S. Aoyagui, J. Am. Chem. Soc., 1985,
107, 6865–6868.
9 P. Anton, P. Koeberle and A. Laschewsky, Prog. Colloid Polym.
Sci., 1992, 89, 56–59.
10 N. Aydogan and N. L. Abbott, Langmuir, 2001, 17, 5703–5706.
11 S. S. Datwani, V. N. Truskett, C. A. Rosslee, N. L. Abbott and
K. J. Stebe, Langmuir, 2003, 19, 8292–8301.
12 K. Tsuchiya, Y. Orihara, Y. Kondo, N. Yoshino, T. Ohkubo,
H. Sakai and M. Abe, J. Am. Chem. Soc., 2004, 126, 12282–
12283.
13 H. Sakai and M. Abe, in Mixed Surfactant Systems, ed. M. Abe
and J. F. Scamehorn, Marcel Dekker, 2nd edn, 2005, New
York, pp. 507–543.
14 M. M. Schmittel, M. Lal, K. Graf, G. Jeschke, I. Suske and
J. Salbeck, Chem. Commun., 2005, 5650–5652.
15 Z. Cheng, B. Ren, M. Gao, X. Liu and Z. Tong,
Macromolecules, 2007, 40, 7638–7643.
16 S. Ghosh, K. Irvin and S. Thayumanavan, Langmuir, 2007, 23,
7916–7919.
17 Y. Liu, P. G. Jessop, M. Cunningham, C. A. Eckert and
C. L. Liotta, Science, 2006, 313, 958–960.
18 L. Scott, T. Robert, J. R. Harjani and P. G. Jessop, RSC Adv.,
2012, 2, 4925–4931.
19 C. I. Fowler, C. Muchemu, R. E. Miller, L. Phan, C. O'Neill,
P. G. Jessop and M. F. Cunningham, Macromolecules, 2011,
44, 2501–2509.
20 C. I. Fowler, P. G. Jessop and M. F. Cunningham,
Macromolecules, 2012, 45, 2955–2962.
21 C. Liang, J. R. Harjani, T. Robert, E. Rogel, D. Kuehne,
C. Ovalles, V. Sampath and P. G. Jessop, Energy Fuels, 2012,
26, 488–494.
22 W. Chu, Pract. Period. Hazard., Toxic, Radioact. Waste
Manage., 2003, 7, 19–24.
23 A. Lottermoser, Trans. Faraday Soc., 1934, 31, 200–204.
24 E. R. Moore and N. A. Lefevre, US Pat., 4,623,678, 1986.
25 E. Penth, US Pat., 5,435,920, 1995.
26 V. Nyren and E. Back, Acta Chem. Scand., 1958, 12, 1305–
1311.
27 M. Rapoport, C. K. Hancock and E. A. Meyers, J. Am. Chem.
Soc., 1961, 83, 3489–3494.
28 Determination of Organic Structures by Physical Methods, ed.
E. A. Braude and F. C. Nachod, Academic Press, 1955.
29 R. A. Peters, Proc. R. Soc. London, Ser. A, 1931, 133, 140–154.
30 R. W. Wakelin, Trans. Faraday Soc., 1938, 34, 1535–1536.
31 K. A. Coltharp and E. I. Franses, Colloids Surf., A, 1996, 108,
225–242.
This journal is © The Royal Society of Chemistry 2014

Paper
32 S. S. Tzocheva, P. A. Kralchevsky, K. D. Danov,
G. S. Georgieva, A. J. Post and
K. P. Ananthapadmanabhan, J. Colloid Interface Sci.,
2012, 369, 274–286.
33 N. T. Hansen, I. Kouskoumvekaki, F. S. Jørgensen, S. Brunak
and S. Ó. Jónsdóttir, J. Chem. Inf. Model., 2006, 46, 2601–
2609.
Published on 03 December 2013. Downloaded by National Chung Hsing University on 12/04/2014 19:39:15.
34 A. Llinàs, J. C. Burley, K. J. Box, R. C. Glen and
J. M. Goodman, J. Med. Chem., 2007, 50, 979–983.
35 K. Urum, T. Pekdemir and M. Çopur, J. Colloid Interface Sci.,
2004, 276, 456–464.
36 M. J. Rosen, Surfactants and Interfacial Phenomena, Wiley,
Hoboken, NJ, 3rd edn, 2004.
37 K. Verschueren, Handbook of environmental data on organic
chemicals, Wiley, New York, 4th edn, 2001.
38 A. Dominguez, A. Fernández, N. González, E. Iglesias and
L. Montenegro, J. Chem. Educ., 1997, 74, 1227–1231.
This journal is © The Royal Society of Chemistry 2014
View Article Online
RSC Advances
39 Triton X-100 Product Information, Sigma Aldrich Chemical
Company, 1999.
40 TritonTM X-100 Surfactant, Form No. 119-01882-1207, The
Dow Chemical Company, 2012.
41 L. Shedlovsky, G. D. Miles and G. V. Scott, J. Phys. Colloid
Chem., 1947, 51, 391–407.
42 A. N. Campbell and G. R. Lakshminarayanan, Can J. Chem.,
1965, 43, 1729–1737.
43 R. Salgado, P. Bandini and A. Karim, J. Geotech. Geoenviron.
Eng., 2000, 126, 451–462.
44 K. D. Pennell, L. M. Abrlola and W. J. Weber Jr, Environ. Sci.
Technol., 1993, 27, 2332–2340.
45 C. Baird, Environmental Chemistry, W. H. Freeman, New
York, 2nd edn, 1998.
46 Environmental Engineering, ed. N. L. Nemerow, F. J. Agardy,
P. Sullivan and J. A. Salvato, John Wiley & Sons, Hoboken,
New Jersey, 2009.
RSC Adv., 2014, 4, 4638–4645 | 4645