The Use of Microemulsion and Flushing Solutions To Remediate Diesel-Polluted Soil

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
1
T. N. C. Dantas, 1M. C. P. A. Moura*, 1A. A. Dantas Neto,
1
F. S. H. T. Pinheiro, 1E. L. Barros Neto
1
Universidade Federal do Rio Grande do Norte -UFRN, Departamento de Engenharia Química.
* 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 of numerous technologies. Among these

Soil and groundwater contamination by non- technologies one cites the use of:
aqueous phase liquids (NAPLs) represents bioremediation, thermal desorption, soil vapor
serious risks to the environment and human extraction, soil washing, soil flushing, and
health. Soil is contaminated by diesel oil and electrokinetic soil remediation (Virkutyte et al.,
other hydrocarbons mainly by accidental 2002). Soil flushing by surfactant solutions to
spillage and leaks from underground storage remove NAPLs is a technique currently used
tanks. According to Roy et al. (1995) (Ouyang et al., 1995). Soil washing process is a
petroleum hydrocarbons are trapped in the soil physical process of pollutant removal
pores due to capillary forces, in the form of accomplished through the rinsing of soil with
non-continuous ganglia. The ganglia are water, surfactants, solvents or nutrients, being
formed due to the non-wetting properties of this process of limited efficiency when realized
NAPLs in the porous media and prevent the as a unique stage of treatment. According to
spreading of NAPLs on the surface of the soil Raghavan et al. (1991), most soil cleaning
matrix. processes involve the mixing of soil with an
The need to remediate hydrocarbon- extracting solution, followed by the separation
contaminated sites has led to the development of the extractant of the solid phase. The
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BRAZILIAN JOURNAL OF PETROLEUM AND GAS
extractant is cleansed of the contaminant and cosurfactant (butan-1-ol), an aqueous phase

recycled as required. (distilled water with or without NaCl) and an
Surfactants can be used for the remediation oil phase (diesel oil). Experiments in batch and
of soils contaminated with hydrocarbons column using the following washing solutions
because they enhance the solubilization and were performed: water, surfactant solutions,
mobilization of hydrophobic compounds and microemulsified systems. The
(Ouyang et al., 1996). Surfactants are microemulsions showed the best results in
amphiphilic molecules that have a hydrophilic contaminant removal and its displacement and
head group (polar phase affinity) and a flux through soil columns were enhanced due
hydrophobic tail (non-polar phase affinity). to its microglobes size.
They have surface activity and can aggregate in
solution to form clusters named micelles above
the critical micelle concentration (CMC) 2. MATERIALS AND METHODS
(Lange, 1999; Roy et al., 1995).
Several studies using aqueous surfactant 2.1 Materials
solutions to remove oily contaminants from soil The surfactant was derived from coconut oil
have been reported and a major obstacle is the (saponified coconut oil – SCO). It was obtained
potential formation of macroemulsions, through a saponification reaction using sodium
resulting in low efficiency due to soil pores hydroxide (NaOH) in a stoichiometric reaction
clogging by its droplets, with sizes that range (1:1 ratio). The surfactant was obtained with
from 1 to 10 µm. A microemulsion is defined yield of ≈ 90% and was used without further
as a system formed by the dispersion of purification.
microdroplets (0.01-0.1 µm) of two immiscible Diesel oil for soil contamination was
liquids, stabilized by an interfacial membrane supplied by Petrobras and was used as
formed by surfactants. Some systems also received. All other chemicals were analytical
require cosurfactants as film stabilizers. In grade. Distilled water (W) was used in all
either case, microemulsions are experiments.
thermodynamically stable, homogeneous and Soil used in column and batch experiments
optically isotropic solutions (Paul and Moulik, was collected in the town of Guamaré – Rio
1997; Oliveira et al., 2004; Shahidzadeh et al., Grande do Norte – Brazil. The soil sample
1999; Moulik and Paul, 1998; Watarai, 1997; passing through a 9 mesh screen was collected
Klier et al., 2000) and characterized (Table 1). All assays were
A cosurfactant is a nonionic molecule that carried out according to a methodology
has the function of stabilizing the proposed by EMBRAPA (1997), except
microemulsified system, by decreasing particle size distribution (ABNT, 1984).
repulsion forces between hydrophilic parts of
the surfactant molecules. Alcohols are 2.2 Determination of the microemulsion
generally used as cosurfactants in composition
microemulsified systems (Valiente and The microemulsions used in remediation
Álvarez, 2001). tests were composed of: surfactant (S),
Many researches have been developed using cosurfactant (C), oil phase (OP - diesel oil), and
surfactant solutions and microemulsions as aqueous phase (AP). To obtain a
washing agents in soil washing processes microemulsion with low viscosity and high
(Ouyang et al., 1995, 1996, 2002; Roy et al., solubilization capacity for organic compounds
1995; Oliveira et al., 2004; Grasso et al., 2001; it was necessary to investigate cosurfactant
Cheah et al., 1998). The use of surfactant nature (butan-1-ol, pentan-1-ol, octan-1-ol and
solutions and microemulsions to remove diesel dodecan-1-ol), cosurfactant/surfactant ratio
from the soil was investigated in this research. (C/S - 0.5, 1.0, and 2.0) and aqueous phase
The microemulsion was composed by a nature (distilled water with or without NaCl).
surfactant (saponified coconut oil), a
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Table 1. Soil properties.

Propriety Value
Bulk density (g.cm-3) 2.35
Particle medium size (µm) 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 pseudoternary phase diagrams were built using
(Figure 1), a point corresponding to a a computational program (Grapher - Version
pseudobinary mixture comprising active matter 1.28).
(C/S) and aqueous solution was selected, with
10% more in aqueous solution than the 2.3 Column Experiments
solubilization point (SP). This point was called Soil samples (20 g) were artificially
titration point (TP) and was used as titration contaminated with diesel oil (1 and 3 wt.%). A
solution for pseudobinary mixtures of C/S-oil polyvinyl chloride column with 3 cm inner
phase (C/S – OP) and aqueous phase-oil phase diameter and 10 cm length was used. A filter
(AP – OP). membrane was placed at the bottom of the
Titrations were made by adding the titration column to retain fine soil particles inside the
solution to the binary mixtures until they turned column. The flushing solutions were pumped
clear. A mass balance was made for each into the soil column so as to allow their
system with the purpose of obtaining the percolation through the soil sample in
titration solution mass added. Points downflow mode (≈ 1.0 mL.min-1). Experiments
corresponding to the microemulsion region were carried out at room temperature (26°C).
limits were obtained from the calculation of the Each experiment was concluded after 50 mL
mass fractions of each constituent and 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.

column. Five flushing solutions were tested: oil concentration in the aqueous phase
distilled water, 0.5 wt.% NaCl solution, 0.5 wt. remained constant. It was found that
% SCO solution (concentration above equilibrium was attained within one hour for all
surfactant critical micelle concentration, solutions.
CMC=0.021 mol.L-1 or 0.15 wt.%),
surfactant/cosurfactant/water solution, and 2.5 Diesel removal analyses
surfactant/cosurfactant/ 0.5 wt.% NaCl To analyze diesel in the effluent, the
solution. All experiments were made in methodology described by Ouyang et al. (1995)
duplicate (see Figure 2, which also depicts was used. Working standards were prepared
batch experiments). (0.01; 0.03; 0.1; 1.0 and 2.0 mg.L-1) by
dissolving diesel in n-hexane aiming to obtain
2.4 Batch experiments the calibration curve of absorbance versus
Batch experiments (Figure 2) were carried diesel concentration. The diesel-in-hexane
out at room temperature in four steps: 1- soil phase was probed by UV-visible
contamination with 1% or 3% diesel oil; 2- soil spectrophotometry (CARY 1E UV-Visible
contact (10 g) with washing solution (25 mL) Spectrophotometer). When using NaCl
in 200 mL Erlenmeyer flasks allowing the solution, surfactant solution or distilled water,
suspension to equilibrate for 1 h in an 1 mL of effluent was mixed with 10 mL of n-
isothermal shaker bath at 26°C (Tecnal - TE hexane and shaken during 5 minutes. When the
053); 3- solid-liquid separation by filtration; 4- W/S/C solution was used the same procedure
diesel oil determination in the aqueous phase. was adopted except that a small amount of
Water, NaCl solution (0.5 wt.%), 0.50% NaCl was added to enhance diesel extraction by
surfactant solutions (above CMC – 0.15 wt.%), n-hexane (Figure 2).
and W/S/C solutions were used as washing
agents. Experiments were carried out at room
temperature. All experiments were made in 3. RESULTS AND DISCUSSIONS
duplicate.
Initial experiments were performed seeking 3.1 Cosurfactant determination – solubility
to determine the best contact time to reach experiments
equilibrium. The same procedure described Medium- and short-carbon-chain alcohols
above was used with each of the studied are the most used cosurfactants in
washing solutions. Typically, 1 mL samples microemulsion systems. In this research four
were taken from each Erlenmeyer flask at cosurfactants were tested, namely butan-1-ol,
predetermined time intervals ranging from 15 pentan-1-ol, octan-1-ol and dodecan-1-ol.
to 120 min. Equilibrium was reached when the
Figure 2. Batch and column experiments.

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 = 26°C).
The system using butan-1-ol as cosurfactant 3.2 Determination of the

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

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 = 26°C).
3.3 Presence of NaCl in the microemulsion affinity, from hydrophilic to hydrophobic. In

aqueous phase Figure 5, only the microemulsion regions are
Experiments were accomplished using an shown, since these are the regions of interest in
NaCl solution (0.5 and 1.0 wt.% NaCl) as this work.
aqueous phase. As can be observed in Figure 5,
the microemulsion region decreased with 3.4 Soil flushing experiments
increasing electrolyte concentration. The Experiments in batch and column were
increase of salinity in microemulsion systems carried out in order to evaluate diesel oil
using ionic surfactants decreases the Winsor IV removal from the soil samples. The following
region (only a microemulsion) and causes the flushing solutions were tested: water, NaCl
formation of a Winsor III region (an aqueous solution, surfactant solution, and
phase at the bottom in equilibrium with a microemulsified systems. Table 2 shows the
bicontinuous microemulsion in the middle results obtained when soil samples artificially
which is also in equilibrium with an oil phase at contaminated with 1% of diesel oil were used.
the top) and a Winsor II region (an aqueous Similar results are shown in Table 3, when
phase in equilibrium with a water-in-oil levels of 3% diesel oil were examined as
microemulsion), due to changes in surfactant 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) E (%)
Solution
Distilled water 100 3.99 3.99 200 9.56 4.78
NaCl solution 100 8.18 8.18 200 17.99 8.99
SCO solution 100 12.83 12.83 200 26.15 13.07
µE(H2O) 100 54.10 54.10 200 113.11 56.55
µE(NaCl) 100 56.27 56.27 200 118.47 59.23
Table 3. Diesel oil removal from soil matrix in batch and column experiments
using artificially-contaminated soil samples (3%).
Washing Batch Experiments Column Experiments
Solution Added (mg) Removed (mg) E (%) Added (mg) Removed (mg) E (%)
Distilled water 300 20.74 6.91 600 42.54 7.09
NaCl solution 300 33.76 11.25 600 73.26 12.21
SCO solution 300 81.20 27.07 600 168.54 28.09
µE(H2O) 300 220.62 73.24 600 446.17 74.36
µE(NaCl) 300 225.27 74.32 600 455.64 75.94

From the data presented in Tables 2 and 3, it REFERENCES

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effected with distilled water and NaCl solution, Técnicas (Brazilian Association for
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4. CONCLUSIONS D.P. Properties and Applications of
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ACKNOWLEDGMENT organolead and gasoline from contaminated
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Tecnológico), a Brazilian agency for scientific Ouyang, Y., Mansell, R. S., Rhue, R. D.
development, for financial support to this Simulated formation and flow of
research. microemulsions during surfactant flushing
of contaminated soil. Water Res., v. 36(1),
p. 33-40, 2002.

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The Use of Microemulsion and Flushing Solutions To Remediate Diesel-Polluted Soil

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BRAZILIAN JOURNAL OF PETROLEUM AND GAS ISSN 1982-0593

THE USE OF MICROEMULSION AND FLUSHING SOLUTIONS

* To whom all correspondence should be addressed.

Keywords: soil cleaning; diesel oil; surfactant; microemulsion remediation

1. INTRODUCTION of numerous technologies. Among these

26 Downloaded from World Wide Web http://www.portalabpg.org.br/bjpg

extractant is cleansed of the contaminant and cosurfactant (butan-1-ol), an aqueous phase

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Table 1. Soil properties.

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

28 Downloaded from World Wide Web http://www.portalabpg.org.br/bjpg

Figure 2. Batch and column experiments.

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The system using butan-1-ol as cosurfactant 3.2 Determination of the

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3.3 Presence of NaCl in the microemulsion affinity, from hydrophilic to hydrophobic. In

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From the data presented in Tables 2 and 3, it REFERENCES

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