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BRAZILIAN JOURNAL OF PETROLEUM AND GAS
ISSN 1982-0593
DANTAS, T. N. C.; MOURA, M. C. P. A.; DANTAS NETO, A. A.; PINHEIRO, F. S. H. T.; BARROS NETO, E. L. THE USE OF MICROEMULSION AND FLUSHING SOLUTIONS TO
REMEDIATE DIESEL-POLLUTED SOIL. Brazilian Journal of Petroleum and Gas. v. 1, n. 1, p. 26-33, 2007.
THE USE OF MICROEMULSION AND FLUSHING SOLUTIONS

TO REMEDIATE DIESEL-POLLUTED SOIL
T. N. C. Dantas, 1M. C. P. A. Moura*, 1A. A. Dantas Neto,
1
F. S. H. T. Pinheiro, 1E. L. Barros Neto
Universidade Federal do Rio Grande do Norte -UFRN, Departamento de Engenharia Qumica.
* To whom all correspondence should be addressed.

Address: Av. Senador Salgado Filho s/n, Lagoa Nova, Natal - RN- Brazil, CEP. 59072-970
Telephone / fax numbers: +55 84 3215-3773 / +55 84 3215-3770
E-mail: carlenise@eq.ufrn.br
Abstract. The applicability of a surfactant derived from coconut oil (saponified coconut
oil SCO) to remove diesel oil from contaminated soil was investigated. This surfactant
was applied in aqueous solutions and in a microemulsion precursory solution
(surfactant/cosurfactant/water). Bench-scale tests were carried out using both column
and batch setups with artificially contaminated soil. Parameters tested, that have
influence
in
microemulsion
formation,
include:
cosurfactant
nature,
cosurfactant/surfactant ratio (C/S), and presence or absence of an electrolyte in the
aqueous phase (NaCl). Upon construction of pseudoternary phase diagrams it was
observed that increasing C/S ratio and presence of electrolyte cause a reduction in the
microemulsion region. Five washing solutions were tested: distilled water, distilled
water with 0.5 wt.% NaCl, surfactant solution (0.5 wt.% SCO above critical micelle
concentration - CMC), and a microemulsion precursory solution with and without NaCl
in its aqueous phase. It was observed that the formation of diesel-in-oil microemulsion
makes easy the removal of contaminants from the used soil. It was found that in batch
experiments a 74% contaminant removal can be achieved and in column experiments up
to 75% diesel oil could be removed, showing the potential applicability of this
surfactant in microemulsion systems for cleaning up contaminated sandy soils.
Keywords: soil cleaning; diesel oil; surfactant; microemulsion remediation
1. INTRODUCTION
Soil and groundwater contamination by nonaqueous phase liquids (NAPLs) represents
serious risks to the environment and human
health. Soil is contaminated by diesel oil and
other hydrocarbons mainly by accidental
spillage and leaks from underground storage
tanks. According to Roy et al. (1995)
petroleum hydrocarbons are trapped in the soil
pores due to capillary forces, in the form of
non-continuous ganglia. The ganglia are
formed due to the non-wetting properties of
NAPLs in the porous media and prevent the
spreading of NAPLs on the surface of the soil
matrix.
The need to remediate hydrocarboncontaminated sites has led to the development
26
of numerous technologies. Among these

technologies one cites the use of:
bioremediation, thermal desorption, soil vapor
extraction, soil washing, soil flushing, and
electrokinetic soil remediation (Virkutyte et al.,
2002). Soil flushing by surfactant solutions to
remove NAPLs is a technique currently used
(Ouyang et al., 1995). Soil washing process is a
physical process of pollutant removal
accomplished through the rinsing of soil with
water, surfactants, solvents or nutrients, being
this process of limited efficiency when realized
as a unique stage of treatment. According to
Raghavan et al. (1991), most soil cleaning
processes involve the mixing of soil with an
extracting solution, followed by the separation
of the extractant of the solid phase. The
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extractant is cleansed of the contaminant and

recycled as required.
Surfactants can be used for the remediation
of soils contaminated with hydrocarbons
because they enhance the solubilization and
mobilization of hydrophobic compounds
(Ouyang et al., 1996). Surfactants are
amphiphilic molecules that have a hydrophilic
head group (polar phase affinity) and a
hydrophobic tail (non-polar phase affinity).
They have surface activity and can aggregate in
solution to form clusters named micelles above
the critical micelle concentration (CMC)
(Lange, 1999; Roy et al., 1995).
Several studies using aqueous surfactant
solutions to remove oily contaminants from soil
have been reported and a major obstacle is the
potential formation of macroemulsions,
resulting in low efficiency due to soil pores
clogging by its droplets, with sizes that range
from 1 to 10 m. A microemulsion is defined
as a system formed by the dispersion of
microdroplets (0.01-0.1 m) of two immiscible
liquids, stabilized by an interfacial membrane
formed by surfactants. Some systems also
require cosurfactants as film stabilizers. In
either
case,
microemulsions
are
thermodynamically stable, homogeneous and
optically isotropic solutions (Paul and Moulik,
1997; Oliveira et al., 2004; Shahidzadeh et al.,
1999; Moulik and Paul, 1998; Watarai, 1997;
Klier et al., 2000)
A cosurfactant is a nonionic molecule that
has the function of stabilizing the
microemulsified system, by decreasing
repulsion forces between hydrophilic parts of
the surfactant molecules. Alcohols are
generally
used
as
cosurfactants
in
microemulsified systems (Valiente and
lvarez, 2001).
Many researches have been developed using
surfactant solutions and microemulsions as
washing agents in soil washing processes
(Ouyang et al., 1995, 1996, 2002; Roy et al.,
1995; Oliveira et al., 2004; Grasso et al., 2001;
Cheah et al., 1998). The use of surfactant
solutions and microemulsions to remove diesel
from the soil was investigated in this research.
The microemulsion was composed by a
surfactant (saponified coconut oil), a
cosurfactant (butan-1-ol), an aqueous phase

(distilled water with or without NaCl) and an
oil phase (diesel oil). Experiments in batch and
column using the following washing solutions
were performed: water, surfactant solutions,
and
microemulsified
systems.
The
microemulsions showed the best results in
contaminant removal and its displacement and
flux through soil columns were enhanced due
to its microglobes size.
2. MATERIALS AND METHODS
2.1 Materials
The surfactant was derived from coconut oil
(saponified coconut oil SCO). It was obtained
through a saponification reaction using sodium
hydroxide (NaOH) in a stoichiometric reaction
(1:1 ratio). The surfactant was obtained with
yield of 90% and was used without further
purification.
Diesel oil for soil contamination was
supplied by Petrobras and was used as
received. All other chemicals were analytical
grade. Distilled water (W) was used in all
experiments.
Soil used in column and batch experiments
was collected in the town of Guamar Rio
Grande do Norte Brazil. The soil sample
passing through a 9 mesh screen was collected
and characterized (Table 1). All assays were
carried out according to a methodology
proposed by EMBRAPA (1997), except
particle size distribution (ABNT, 1984).
2.2 Determination of the microemulsion
composition
The microemulsions used in remediation
tests were composed of: surfactant (S),
cosurfactant (C), oil phase (OP - diesel oil), and
aqueous phase (AP). To obtain a
microemulsion with low viscosity and high
solubilization capacity for organic compounds
it was necessary to investigate cosurfactant
nature (butan-1-ol, pentan-1-ol, octan-1-ol and
dodecan-1-ol), cosurfactant/surfactant ratio
(C/S - 0.5, 1.0, and 2.0) and aqueous phase
nature (distilled water with or without NaCl).
27

Table 1. Soil properties.

Propriety
Value
Bulk density (g.cm-3)
2.35
Particle medium size (m)
691.31
Clay (%)
3.53
Silt (%)
10.19
Fine sand (%)
35.62
Medium sand (%)
45.89
Coarse sand (%)
4.77
Acidity (cmol.kg-1)*
0.505
Organic carbon (dag.kg-1)**
0.432
Organic matter (dag.kg-1)
0.745
Nitrogen content (dag.kg-1)
0.06
Phosphorus content (mg.L-1)
0.0025
* Exchangeable acidity (H+ and Al+3) KCl
** dag.kg-1 = % (m/m) - 1 decagram (dag) = 10 g
To obtain the pseudoternary phase diagrams

(Figure 1), a point corresponding to a
pseudobinary mixture comprising active matter
(C/S) and aqueous solution was selected, with
10% more in aqueous solution than the
solubilization point (SP). This point was called
titration point (TP) and was used as titration
solution for pseudobinary mixtures of C/S-oil
phase (C/S OP) and aqueous phase-oil phase
(AP OP).
Titrations were made by adding the titration
solution to the binary mixtures until they turned
clear. A mass balance was made for each
system with the purpose of obtaining the
titration solution mass added. Points
corresponding to the microemulsion region
limits were obtained from the calculation of the
mass fractions of each constituent and
pseudoternary phase diagrams were built using

a computational program (Grapher - Version
1.28).
2.3 Column Experiments
Soil samples (20 g) were artificially
contaminated with diesel oil (1 and 3 wt.%). A
polyvinyl chloride column with 3 cm inner
diameter and 10 cm length was used. A filter
membrane was placed at the bottom of the
column to retain fine soil particles inside the
column. The flushing solutions were pumped
into the soil column so as to allow their
percolation through the soil sample in
downflow mode ( 1.0 mL.min-1). Experiments
were carried out at room temperature (26C).
Each experiment was concluded after 50 mL
of flushing solution were passed through the
Figure 1. Pseudoternary phase diagram showing the titration (TP) and

solubilization (SP) points and the mixtures C/S-OP and AP-OP
used to delimitate the microemulsion region.
28

column. Five flushing solutions were tested:

distilled water, 0.5 wt.% NaCl solution, 0.5 wt.
% SCO solution (concentration above
surfactant critical micelle concentration,
CMC=0.021 mol.L-1
or
0.15 wt.%),
surfactant/cosurfactant/water solution, and
surfactant/cosurfactant/
0.5 wt.%
NaCl
solution. All experiments were made in
duplicate (see Figure 2, which also depicts
batch experiments).
2.4 Batch experiments
Batch experiments (Figure 2) were carried
out at room temperature in four steps: 1- soil
contamination with 1% or 3% diesel oil; 2- soil
contact (10 g) with washing solution (25 mL)
in 200 mL Erlenmeyer flasks allowing the
suspension to equilibrate for 1 h in an
isothermal shaker bath at 26C (Tecnal - TE
053); 3- solid-liquid separation by filtration; 4diesel oil determination in the aqueous phase.
Water, NaCl solution (0.5 wt.%), 0.50%
surfactant solutions (above CMC 0.15 wt.%),
and W/S/C solutions were used as washing
agents. Experiments were carried out at room
temperature. All experiments were made in
duplicate.
Initial experiments were performed seeking
to determine the best contact time to reach
equilibrium. The same procedure described
above was used with each of the studied
washing solutions. Typically, 1 mL samples
were taken from each Erlenmeyer flask at
predetermined time intervals ranging from 15
to 120 min. Equilibrium was reached when the
oil concentration in the aqueous phase

remained constant. It was found that
equilibrium was attained within one hour for all
solutions.
2.5 Diesel removal analyses
To analyze diesel in the effluent, the
methodology described by Ouyang et al. (1995)
was used. Working standards were prepared
(0.01; 0.03; 0.1; 1.0 and 2.0 mg.L-1) by
dissolving diesel in n-hexane aiming to obtain
the calibration curve of absorbance versus
diesel concentration. The diesel-in-hexane
phase
was
probed
by
UV-visible
spectrophotometry (CARY 1E UV-Visible
Spectrophotometer). When using NaCl
solution, surfactant solution or distilled water,
1 mL of effluent was mixed with 10 mL of nhexane and shaken during 5 minutes. When the
W/S/C solution was used the same procedure
was adopted except that a small amount of
NaCl was added to enhance diesel extraction by
n-hexane (Figure 2).
3. RESULTS AND DISCUSSIONS
3.1 Cosurfactant determination solubility
experiments
Medium- and short-carbon-chain alcohols
are the most used cosurfactants in
microemulsion systems. In this research four
cosurfactants were tested, namely butan-1-ol,
pentan-1-ol, octan-1-ol and dodecan-1-ol.
Figure 2. Batch and column experiments.
29

Figure 3. Pseudoternary phase diagrams showing the microemulsion region for the systems using SCO
as surfactant and butan-1-ol or pentan-1-ol as cosurfactant (T = 26C).
The system using butan-1-ol as cosurfactant

showed a solubility point around 35 wt.% AP
and 65 wt.% C/S. The system using pentan-1-ol
as cosurfactant presented low solubility point
(70.2 wt.% AP and 29.8 wt.% C/S) and, when
octan-1-ol and dodecan-1-ol were used, the C/S
mixture was insoluble. It could be observed
that an increase in the length of the cosurfactant
carbon chain lead to a decrease in the solubility
of the active material (C/S) in the aqueous
phase (Figure 3). This effect is demonstrated in
Figure 3, whereby the microemulsion region
(E) formed by the butan-1-ol system is greater
than that formed by the pentan-1-ol system. In
view of this, butan-1-ol was the cosurfactant
chosen to be applied in soil remediation
experiments.
3.2
Determination
of
the
Cosurfactant/Surfactant ratio
To evaluate the C/S ratio influence on the
microemulsion region only butan-1-ol was used
as cosurfactant. The pseudoternary diagrams
for systems using C/S ratio equal to 0.5, 1.0
and 2.0 are shown in Figure 4. All studied
systems showed a well-defined microemulsion
region. The C/S ratio equal to 0.5 has been
selected in batch and column experiments due
to the presence of a higher amount of
surfactant, an important agent in oil removal
processes, and a lower amount of cosurfactant,
which, in spite of being biodegradable,
represents a pollutant for the soil matrix.
Figure 4. Pseudoternary phase diagrams showing the microemulsion region for the systems using SCO
as surfactant and butan-1-ol (BUT) as cosurfactant in C/S ratios
equal to 0.5, 1.0 and 2.0 (T = 26C).
30

Figure 5. Pseudoternary phase diagrams showing the microemulsion regions for the systems using SCO
as surfactant and water, 0.5% NaCl solution or 1.0% NaCl
solution as aqueous phase (T = 26C).
3.3 Presence of NaCl in the microemulsion

aqueous phase
Experiments were accomplished using an
NaCl solution (0.5 and 1.0 wt.% NaCl) as
aqueous phase. As can be observed in Figure 5,
the microemulsion region decreased with
increasing electrolyte concentration. The
increase of salinity in microemulsion systems
using ionic surfactants decreases the Winsor IV
region (only a microemulsion) and causes the
formation of a Winsor III region (an aqueous
phase at the bottom in equilibrium with a
bicontinuous microemulsion in the middle
which is also in equilibrium with an oil phase at
the top) and a Winsor II region (an aqueous
phase in equilibrium with a water-in-oil
microemulsion), due to changes in surfactant
affinity, from hydrophilic to hydrophobic. In

Figure 5, only the microemulsion regions are
shown, since these are the regions of interest in
this work.
3.4 Soil flushing experiments
Experiments in batch and column were
carried out in order to evaluate diesel oil
removal from the soil samples. The following
flushing solutions were tested: water, NaCl
solution,
surfactant
solution,
and
microemulsified systems. Table 2 shows the
results obtained when soil samples artificially
contaminated with 1% of diesel oil were used.
Similar results are shown in Table 3, when
levels of 3% diesel oil were examined as
contaminant.
Table 2. Diesel oil removal from soil matrix in batch and column experiments using
artificially-contaminated soil samples (1%).
Batch Experiments
Column Experiments
Washing
Added (mg) Removed (mg) E (%)
Added (mg)
Removed (mg)
Solution
Distilled water
100
3.99
3.99
200
9.56
NaCl solution
100
8.18
8.18
200
17.99
SCO solution
100
12.83
12.83
200
26.15
E(H2O)
100
54.10
54.10
200
113.11
E(NaCl)
100
56.27
56.27
200
118.47
Table 3. Diesel oil removal from soil matrix in batch and column experiments
using artificially-contaminated soil samples (3%).
Batch Experiments
Column Experiments
Washing
Solution
Added (mg) Removed (mg) E (%)
Added (mg)
Removed (mg)
Distilled water
300
20.74
6.91
600
42.54
NaCl solution
300
33.76
11.25
600
73.26
SCO solution
300
81.20
27.07
600
168.54
E(H2O)
300
220.62
73.24
600
446.17
E(NaCl)
300
225.27
74.32
600
455.64
E (%)
4.78
8.99
13.07
56.55
59.23
E (%)
7.09
12.21
28.09
74.36
75.94
31

From the data presented in Tables 2 and 3, it

can be observed that only a slight removal was
effected with distilled water and NaCl solution,
due only to the oil displacement from the soil
granules. When surfactant solutions were used
in batch experiments, the systems turned very
turbid due to the solubilization of organic
compounds that are present in the soil matrix, a
fact that inhibits oil solubilization. In column
experiments the flow rate was strongly reduced
due to emulsion formation, causing pore
clogging by emulsion droplets. In batch and
column experiments using W/S/C solutions,
high removal was observed due to the
formation of microemulsions, enabled by very
low interfacial tensions between the diesel oil
and the W/S/C solution, resulting in oil
solubilization and the elimination of any
clogging of soil pores.
4. CONCLUSIONS
This study demonstrates that a surfactant
derived from coconut oil can be used
successfully in the remediation of dieselcontaminated sandy soil. Column and batch
experiments
showed
that
Surfactant/Cosurfactant/Aqueous
Phase
solutions (S/C/AP(H2O) and S/C/AP(NaCl))
represent a good alternative due to the
formation of microemulsions, resulting in high
removal efficiency, caused by a very low
interfacial tension between the diesel oil and
the AP/S/C solution, which in turn promotes oil
solubilization and inhibition of any clogging of
soil pores. On the other hand, it could also be
concluded that emulsions may be formed when
solutions containing only surfactants are used,
making difficult the use of such mixtures in soil
remediation.
ACKNOWLEDGMENT
The authors are grateful to CNPq (Conselho
Nacional de Desenvolvimento Cientfico e
Tecnolgico), a Brazilian agency for scientific
development, for financial support to this
research.
32
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1996.
Ouyang, Y., Mansell, R. S., Rhue, R. D.
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Roy, D.; Kommalapati, R. R.; Valsaraj, K. T.;
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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

THE USE OF MICROEMULSION AND FLUSHING SOLUTIONS

Universidade Federal do Rio Grande do Norte -UFRN, Departamento de Engenharia Qumica.

* To whom all correspondence should be addressed.

of numerous technologies. Among these

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

extractant is cleansed of the contaminant and

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cosurfactant (butan-1-ol), an aqueous phase

BRAZILIAN JOURNAL OF PETROLEUM AND GAS

Table 1. Soil properties.

To obtain the pseudoternary phase diagrams

pseudoternary phase diagrams were built using

Figure 1. Pseudoternary phase diagram showing the titration (TP) and

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

column. Five flushing solutions were tested:

oil concentration in the aqueous phase

Figure 2. Batch and column experiments.

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

The system using butan-1-ol as cosurfactant

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

3.3 Presence of NaCl in the microemulsion

affinity, from hydrophilic to hydrophobic. In

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

From the data presented in Tables 2 and 3, it

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS

Paul, B.K. and Moulik, S.P. Microemulsions:

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Shahidzadeh, N.; Bonn, D.; Aguerre-Charol,

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