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Environ. Sci. Technol.

1997, 31, 670-675

Soil Washing Potential of a Natural belonging to the genus Sapindaceae that appear to have
potential for the remediation of contaminated soils. These
Surfactant plants produce saponaceous substances called saponins,
which form lather or foam in water (9, 10). Sapindus
mukurossi, Sapindus trifoliatus, Sapindus laurifolius, and
D . R O Y , * , R . R . K O M M A L A P A T I , , Sapindus emarginatus plants are widely grown in India and
S . S . M A N D A V A , ,| K . T . V A L S A R A J , A N D other tropical and subtropical regions of Asia, and their fruits
W . D . C O N S T A N T , are known by the common name Ritha or soapnut. About
Department of Civil & Environmental Engineering, 56% of the fruit is pericarp, and the balance is the seed (11).
Polytechnic University, Brooklyn, New York 11201, and These natural products have been traditionally used as a
Hazardous Waste Research Center, 3418 CEBA Building, detergent for fabric washing and bathing and in folk medicine.
Department of Civil & Environmental Engineering, and The recorded external uses of this natural surfactant as a
Department of Chemical Engineering, Louisiana State washing soap does not cite any toxic effects on human skin
University, Baton Rouge, Louisiana 70803
and eyes (12).
Several researchers have isolated and identified the
saponins from the fruit pericarps of the plants of genus
Biodegradable natural surfactants obtained from plants Sapindus (13-17). Saponins are complex substances and
are essentially glycosides with their aglycones related to either
can be an attractive alternative to synthetic surfactants in
sterols or triterpenes. Saponin fraction was determined to
the remediation of contaminated soils. In this research, be 10.1% of the weight of the pericarp and 6.1% based on the
a plant-based surfactant obtained from the fruit pericarp of weight of the fruit (15). Extraction of the fruit pericarp with
Sapindus mukurossi, a tree generally grown in tropical water has been the most commonly used method both for
regions of Asia, is tested. A simple and economical method scientific and domestic uses such as washing hair and fabric.
for the preparation of the surfactant is developed. An The aqueous solution thus obtained can be purified by
empirical formula for the surfactant was determined to be isolating the saponin fraction.
(C26H31O10)n. The aqueous solubilities of hexachlorobenzene Research work on these plant products primarily focused
(HCB) and naphthalene in the natural surfactant solutions on isolation and identification of the chemical constituents
were found to vary linearly with the concentration of the of the saponin fraction of the fruit extract and to a lesser
surfactant showing trends comparable to that of typical com- extent on the application of these fruits as folk medicines.
However, no scientific research exploring their application
mercial surfactants. Natural surfactant solutions were
for soil remediation has been found in literature. Preliminary
also employed for flushing HCB from one-dimensional soil experiments conducted in our laboratory using natural
columns. HCB recoveries after 12 pore volumes of flushing surfactant solutions for the remediation of soils contaminated
with 0.5 and 1% natural surfactant solutions were 20 and 100 with naphthalene and hexachlorobenzene indicated that these
times more than that recovered by water flooding. These solutions can desorb and solubilize significant amounts of
promising results warrant further research to establish the these hydrophobic compounds. Also, these natural surfactant
usefulness of plant-based surfactants for soil washing solutions were noted to enhance the growth of soil micro-
applications. organisms under aerobic and anaerobic conditions by Ko-
mmalapati and Roy (18, 19). This paper focuses on evaluating
the potential of this plant-based surfactant for soil flushing.
Introduction
Surfactants have been shown to increase the removal of Experimental Section
contaminants from laboratory soil columns by solubilizing Materials. Dry fruits of Sapindus mukorossi were procured
significant amounts of the contaminants (1-5). They can from India. These fruits are golden brown in color and
also be useful in mobilizing non-aqueous phase liquids from globular in shape with a diameter between 1 and 3 cm. After
aquifers by decreasing the interfacial tension between the removing the seed, the outer pericarps were dried in an oven
organic and water phases (6, 7). Use of surfactant solutions at 50 C for about 2 days. The pericarps were ground and
for soil washing has two advantages: (i) surfactant molecules sieved through U.S. Standard No. 20 sieve (840 m).
tend to concentrate at the organic/aqueous interfaces and Hexachlorobenzene (HCB), an aromatic chlorinated hydro-
lower the interfacial tension considerably and (ii) surfactant carbon, and naphthalene, a polycyclic aromatic hydrocarbon,
molecules also form aggregates known as micelles at con- were used as test compounds. These chemicals obtained
centrations beyond the critical micelle concentration (cmc) from Aldrich Chemical Company (Milwaukee, WI) were 99%
that can solubilize hydrophobic organic compounds (HOCs). pure and used as supplied.
Mostly synthetic surfactants are currently being tested for An uncontaminated soil from a Superfund site near Baton
the remediation of subsurface soils contaminated with Rouge, LA, was air-dried, homogenized, and kept in an oven
complex wastes at hazardous waste sites (3, 8). overnight at 105 C for drying. Soil was ground, and the
In our recent search for biodegradable natural surfactants, fraction passing U.S. Standard No. 10 (2 mm) sieve was used
we have identified a class of surfactants derived from plants for the soil flushing experiments. This soil is classified as a
sandy loam and has a very low organic matter content (e0.3%).
* Corresponding author fax: 718-260-3433; e-mail: droy@duke.
poly.edu. Preparation of Natural Surfactant Solutions. Based on
Department of Civil & Environmental Engineering, Polytechnic the available literature, water, methanol, ethanol, and a
University. benzene:methanol (1:3) mixture were examined as solvents
Hazardous Waste Research Center, Louisiana State University.
Present address: Rust Environment & Infrastructure, Greenville,
for preparing the natural surfactant solutions. The powder
was added to solvents and stirred for 3 h at room temperature.
SC 12345.
| Department of Civil & Environmental Engineering, Louisiana State The mixture was centrifuged at 10 000 rpm for 45 min, and
University. the supernatant was filtered through a 0.44-mm prefilter
Department of Chemical Engineering, Louisiana State University. followed by a metricel 0.45-m membrane filter (Gelman

670 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 31, NO. 3, 1997 S0013-936X(96)00181-2 CCC: $14.00 1997 American Chemical Society
Scientific, Ann Arbor, MI) in sequence. The filtrate was
allowed to evaporate on a water bath at 70 C. The dry paste
obtained was re-dissolved in water and used as stock solution.
A 10% natural surfactant solution was prepared by extracting
10 g of fruit pericarp powder in 100 mL of deionized water
in a similar way except that the last two steps, i.e., evaporating
the filtrate and redissolving it in water, were eliminated.
Surface Tension, Viscosity, and UV Absorbance Mea-
surements. Surface tension measurements of aqueous
solutions of the surfactant were made using a processor
tensiometer K14 (Kruss GmbH, Hamburg, Germany). Vis-
cosity measurements were made using a Bohlin VOR rhe-
ometer system (Bohlin Instruments International AB, Lund,
Sweden). The UV-visible absorbance spectrum of natural
surfactant solutions was obtained using HP 8452A diode array
spectrophotometer with HP 89531A-UV-VIS software
(Hewlett-Packard Company, Wilmington, DE).
Solubility Experiments. Aqueous solubility experiments
were performed in Erlenmeyer flasks using several concen-
trations of surfactant in the presence of excess quantities of
FIGURE 1. Variation of HCB solubility with soapnut concentration
HCB or naphthalene crystals. The flasks were equilibrated for extracts of several solvents.
for about 36 h, and the samples were centrifuged in Teflon
tubes for 15 min at 15 000 rpm. The supernatant was extracted mixture at room temperature. Ethanol extracted the least
and analyzed for HCB or naphthalene. (59.5%) and had a light yellowish golden color, whereas water
Soil Flushing Experiments. Glass columns (10 cm long extracted the most (71.2%) and had a very dark golden color.
and 5.75 cm in diameter) with a stainless steel top and bottom Methanol and methanol:benzene mixture extracted 68.6%
were used for all soil flushing experiments (7). To prevent and 63.2%, respectively, and acquired colors between those
soil from being washed out of the column and to distribute of water and ethanol extracts. Figure 1 shows the variation
the flow uniformly, the outlet and inlet ends of the column of HCB solubility with concentration of surfactant for the
were fitted with fine wire mesh sandwiched between two four solvents. The lines represent the regression data, and
coarse wire meshes. Soil was contaminated by dissolving an the points indicate the experimental data. The solubility of
appropriate quantity of HCB in petroleum ether and mixing HCB increased with an increase in surfactant concentration
it with a known weight of soil. This slurry was mixed for all extracts. HCB solubility at any soapnut concentration
thoroughly and the ether was allowed to evaporate slowly. was highest for methanol extract, followed by methanol:
The dry soil was transferred into a bottle and tumbled for benzene mixture, ethanol, and water extract. The differences
about 1 week before the experiments. A soil packing between the different extracts were larger at higher concen-
procedure was adopted to achieve a bulk density (1.6 g/cm3) trations (5% and 10%), and the variation decreased with a
similar to that observed in the field (7). The column packed decrease in concentration. The variation between the HCB
with contaminated soil was saturated with deionized water. solubilities of different extracts is not significant at the 95%
Experiments were conducted in the downflow mode with confidence level for concentrations up to 2.5% with Tukey
water and natural surfactant solutions at a flow rate of 2.5 multiple comparison method. Natural surfactant concentra-
mL/min (pore water velocity ) 0.24 cm/min). The effluent tions beyond 2.5% may also pose practical limitations (10).
samples were collected and analyzed for HCB. Hence, for simplicity in preparation, the use of water to extract
Analysis of Hexachlorobenzene. The traditional liquid- fruit pericarp is recommended for field applications.
liquid extraction for HCB analysis (EPA Method 612) did not (b) Mixing Time and Temperature. The optimum mixing
work effectively in the presence of surfactant solutions. time and temperature required to prepare the surfactant were
Commercially available SepPak C18 cartridges (Millipore determined experimentally by measuring the solubility of
Corporation, Milford, MA) were used for extracting HCB from naphthalene in 10% water extracts for several mixing times
aqueous solutions (10). The cartridges were activated by (1-12 h) at room temperature. The highest naphthalene
passing 5 mL of deionized (DI) water, 5 mL of methanol, and solubility was obtained for mixing times of 1 and 3 h. The
5 mL of DI water again. The sample was eluted through the solubility of naphthalene progressively decreased as the
cartridge at a rate of 5 mL/min followed by a wash with 5 mL mixing time was increased beyond 3 h. In the subsequent
of DI water. The cartridge was then eluted with 5 mL of work, a mixing time of 3 h was adopted. The variation in
hexane, which was collected and analyzed for HCB on a HP naphthalene solubility for several mixing temperatures in the
5890 Series II gas chromatograph (Hewlett-Packard Company, range of 20-50 C was studied. The maximum solubility of
Wilmington, DE) fitted with a HP 7673 autosampler and Ni63 naphthalene was observed at 28 C, and the solubility at room
electron capture detector (ECD). The GC was equipped with temperature was only about 8% less than the maximum
a 30 m PTE-5 capillary column, with a 0.32 mm internal solubility. Thus, it was concluded that extraction of soapnut
diameter and 1.0 m film thickness (Supelco Inc., Bellefonte, into water at room temperature using a mixing time of 3 h
PA.). The chromatographic conditions were as follows: 1 L with subsequent centrifugation and filtration with 0.45 m
splitless injection; injection temperature 275 C; temperature metricel filter was satisfactory. By using water as the solvent,
program 50 C for 1 min to 270 C at 10 C/min, and hold for two additional steps (evaporation of solvent and redissolution)
3 min; and ECD temperature 325 C. Minimum detection were avoided. The only byproduct in the preparation of
limit for the method was 1 pg. Recovery of HCB using this natural surfactant solutions is the un-extracted residue, which
method was found to be 93.7% with a standard deviation of is about 30% of the total mass. The simple and safe method
2.2% (10). of preparation for this natural surfactant will definitely be an
added advantage for its application in the real world.
Results and Discussion Several experiments were conducted to study the effect of
Preparation of Natural Surfactant Solutions. (a) Solvent refrigeration storage time on the performance of natural
Selection. The fruit pericarp powder was extracted using surfactant solutions. Refrigeration of extracts up to 6 days
either water, methanol, ethanol, or a methanol:benzene (3:1) did not change significantly the solubilizing capacity of natural

VOL. 31, NO. 3, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 671


FIGURE 2. Determination of cmc for natural surfactant solutions
using surface tension measurements.

surfactant solutions. However, surfactant solutions that were


not refrigerated became cloudy within 2 days, indicating
substantial microbial growth.
Characterization of Natural Surfactant Solutions. (a)
Properties. The natural surfactant was characterized by
determining pH, chemical oxygen demand (COD), total
organic carbon (TOC), total nitrogen, and total phosphorous.
All the values were measured for a 10% surfactant solution.
The COD and TOC of a 10% surfactant solution were 124 and
41 g/L, respectively. The nitrogen and phosphorous content
of natural surfactant solutions were non-detectable using FIGURE 3. Solubility of (a) hexachlorobenzene and (b) naphthalene
Standard Methods (20). The pH of the surfactant solution in natural surfactant solutions.
varied from 7.2 to 4.5 as the concentration increased from
0.005% to 1% and did not vary beyond 1%. The acidic nature 0.0005-10%. It is apparent from this figure that there is a
of the solution could be due to the hydrolysis of the glycosides sharp break in the surface tension curve in the concentration
present in the fruit pericarps (16). range 0.08-0.1%. As the concentration of natural surfactant
The empirical formula of a compound can be determined increased from 0.0005 to 0.1%, surface tension dropped
either from the percentage composition of each element or steadily, and beyond 0.1% the value remained stable at about
from the oxidation of the compound. The latter method is 35 mN/m. This value is very similar to the range of 30-40
used in this study due to its simplicity. Knowing the COD, mN/m reported for several commercial surfactants (2, 3).
TOC, nitrogen, phosphorous, and total weight of the organic The viscosity of natural surfactant solutions at a low con-
compound, an empirical formula was calculated from the centration (0.01%) was significantly higher than that of water,
generalized oxidation half-reaction for an organic (10). The and it reached a minimum when the concentration increased
empirical formula for natural surfactant solutions was found from 0.01% to 0.1%. At low surfactant concentration, the
to be (C26H31O10)n, where n is a constant and needs to be molecules are present in the monomeric form, and the
determined either from vapor density or by a cryoscopic hydrophilic moieties of surfactant are surrounded by ordered
method. The total carbon content of natural surfactant water molecules resulting in an increase in the viscous
solutions expressed as percent of total weight of the com- resistance. However, the formation of micelles releases the
pound was 60.6%. Row and Rukmini (16, 17) reported that ordered water molecules and causes an abrupt change in
the carbon content was 57.8% and 61.8% and a molecular viscosity. Viscosity measurements also indicate that the cmc
formula of C52H84O212H2O and C47H76O17 for the saponin of natural surfactant is 0.1%, thus confirming the cmc value
fraction of S. mukurossi and S. emarginatus, respectively. The obtained from surface tension measurements. When the
empirical formula obtained in this study incorporates all the natural surfactant concentration was increased beyond cmc
water-soluble constituents of the compound. Natural sur- (0.1%), the viscosity increased again due to the formation of
factant solutions are mixtures of complex organic compounds, more micelles and the resultant intermicellar interactions.
and mass spectrometry was not helpful since the extract had Measurement of Natural Surfactants Using UV Absor-
to be further purified significantly. The empirical formula bance. Natural surfactants, a mixture of saponins, glycosides,
obtained in this study gives a fair idea of the ratio of carbon, and other sugars, are fairly difficult to quantify accurately
hydrogen, and oxygen in natural surfactant solutions. without chromatographic separation of individual com-
(b) Critical Micelle Concentration. A very fundamental pounds. However, several researchers used UV absorption
and important property of surfactants is micelle formation, as a surrogate measure for selected organic constituents in
which affects almost every measurable physical property that freshwater, wastewater, and salt water (22).
depends on size or number of particles in solution such as Natural surfactant solutions of several concentrations were
conductivity, surface tension, osmotic pressure, and viscosity. analyzed with a UV/visible spectrophotometer. The absor-
All these properties will show a break in the curve plotted bance at any wavelength increased with an increase in
against the concentration of surfactant in the region of the surfactant concentration. The concentrations of natural
cmc (21). Figure 2 shows the variation of surface tension surfactant and absorbance at wavelengths 252 and 292 nm
with the natural surfactant concentration in the range of were correlated, and the resulting equations are

672 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 31, NO. 3, 1997


A252 ) 0.05 + 2.31C (R 2 ) 0.992) (1)

A292 ) 0.002 + 1.675C (R 2 ) 0.994) (2)

where A is absorbance and C is concentration of natural


surfactant in weight percent. The strong correlation between
UV absorbance and natural surfactant concentration (R2 >
0.99) suggests that these equations can be employed to
determine the concentration of natural surfactant solutions.
The correlations are valid in the range of 0.1-1.2% and 0.1-
1.5% for wavelengths 252 and 292 nm, respectively.
Solubility of Hexachlorobenzene and Naphthalene in
Natural Surfactant Solutions. Figure 3a shows the variation
in HCB solubility in natural surfactant solutions in the
concentration range of 0.1-10%. Four measurements at each
concentration are indicated by points, and the regression fit
is represented by a line. Solubility of HCB in 10% natural
surfactant solution increased several hundred times more
than that in water. There appeared to be a linear relationship
between solubility and natural surfactant concentration up
to 10% surfactant concentration. The linearity between HCB
solubility and surfactant concentration beyond cmc has been
well established for commercial surfactants (2, 4, 21, 23). The
slope of the regression line represents the maximum amount
of HCB per mass of surfactant in equilibrium with solid phase
HCB at standard temperature and pressure. The slope of the
solubility curve can be used to calculate the solubilization
ratio (SR), defined as

Co - Co*
SR )
Cs - Cs*
FIGURE 4. Comparison of natural surfactant solutions with com-
where Co and Co* are the concentrations of organic in a mercial surfactants: (a) hexachlorobenzene and (b) naphthalene.
surfactant solution at any surfactant concentration and at
critical micellar concentration (in g/g), respectively, and Cs
water to solubilize 1 mg of organic. The results of HCB
and Cs* are the concentration of surfactant and the cmc of
solubility in different surfactants are presented in Figure 4.
the surfactant (in g/g), respectively. One could also use molar
Brij 30, POE 10-LE, and Tween 85 seem to be very effective
concentrations and calculate the molar solubilization ratio
in solubilizing HCB as only a fraction of 1 g of surfactant was
(2). Since the surfactant concentration is expressed as percent
needed to solubilize 1 mg. About 2-3 g of Brij 35, Tween 20,
(w/w), the solubility units are converted from micrograms
Tween 80, and Exxal F 5715 was needed to solubilize a
per liter to grams per gram, and the solubilization ratio is
comparable quantity of HCB. Triton X-705 and Pluronic P-65
calculated. For natural surfactant and HCB, the solubilization
were less effective, requiring approximately 51 and 83 g,
ratio is found to be in the range of 8.1 10-5 to 9.5 10-5.
respectively, to solubilize 1 mg of HCB. In contrast, about
Figure 3b shows solubility of naphthalene in natural
10.5 g of soapnut and about 5.5 g of SDS were required to
surfactant solutions. Naphthalene solubility also was directly
solubilize 1 mg of HCB.
proportional to the natural surfactant concentration in the
range of 0.1-10%. This confirmed the general trend of linear A similar comparison of naphthalene solubility in different
proportionality of solubilization of a hydrophobic compound surfactants is presented in Figure 4b. To solubilize 1 mg of
by a surfactant above its cmc. The solubilization ratio for naphthalene in 1 L of water required about 215, 52, and 53
natural surfactant and naphthalene was determined to be mg of soapnut powder, sodium dodecyl sulfate (SDS), and
4.8 10-3 g/g. It is believed that a partition-like interaction sodium dodecyl benzene sulfonate (SDBS), respectively. Only
of the hydrophobic solute with the microscopic organic about 30 mg of non-ionic surfactant Tergitol and 15 mg of
environment of dissolved organic molecules is responsible cationic surfactant hexadecyl trimethyl ammonium bromide
for the increased solubility of the solute. Natural surfactant, (HTAB) are required to solubilize 1 mg of naphthalene. In
due to its constituents, may behave very similarly to natural all these comparisons, it should be noted that only 70% of the
organic matter and thus improve the solubility of solutes. soapnut is dissolved in water, which makes the net weight of
This increase in solubility can be in addition to what was soapnut powder requirement for solubilizing 1 mg of HCB
provided by saponins, the fraction responsible for the and naphthalene as 7.5 g and 150 mg, respectively.
surfactant properties of the fruit extract. Application of Natural Surfactant Solutions to Soil
Comparison of Natural and Commercial Surfactant Flushing. Results of soil flushing experiments are sum-
Solutions. Solubility of HOCs in natural surfactant solutions marized in Figure 5a,b for 0.5% and 1% natural surfactant
exhibited a similar pattern as typically observed for com- solutions, respectively. The columns were packed with soil
mercial surfactants showing a linear increasing trend of contaminated to a level of approximately 2, 70, and 110 mg
solubility with an surfactant concentration. Roy et al. (24) of HCB/kg of soil. It is clear from these graphs that the removal
reported the solubility of naphthalene in four commercial of HCB during the first pore volume after saturation of the
surfactants, and Jafvert et al. (23) used 10 different surfactants column was practically negligible. HCB concentration in the
to solubilize HCB in aqueous solutions. The solubility effluent increased as more surfactant was pumped through
parameter (mmol of organic/mol of surfactant) reported in the column. During the first pore volume, the saturation
these studies is used for comparison. The comparison is water was replaced with surfactant solution. The surfactant
done on the basis of grams of surfactant required in 1 L of molecules pumped during the initial pore volumes are known

VOL. 31, NO. 3, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 673


FIGURE 5. Recovery of HCB from one-dimensional soil columns FIGURE 6. Effect of natural surfactant concentration on the recovery
flushed with natural surfactant solutions: (a) 0.5% and (b) 1% natural of HCB from one-dimensional soil columns (a) 2 mg/kg and (b) 90
surfactant. mg of HCB/kg of soil.

to undergo adsorption onto soil, and the effective surfactant


concentration monitored by UV adsorption in the effluent
was considerably lower than that in the influent. The
adsorption of surfactant continued for about 3-4 pore
volumes before the effluent surfactant concentration reached
a maximum. HCB concentrations increased steadily after
the first pore volume and approached the maximum value
by the fifth pore volume. This maximum concentration was
about 80% of the HCB solubility in the aqueous natural
surfactant solution of the corresponding concentration. HCB
concentration in the effluent remained fairly constant for the
remainder of the experiment. The removal appeared to be
limited by mass transfer from the adsorbed phase to the
aqueous phase at low contamination levels (2 mg of HCB/kg
of soil), since HCB concentration in the effluent was only a
small fraction of its solubility. Natural surfactant solution of
1% concentration recovered a total of 110 and 1000 g of
HCB in 12 pore volumes from soil contaminated with 2 and
80 mg of HCB/kg of soil, respectively. As the contamination
level increased, HCB recoveries increased, but the recoveries
were limited by the HCB solubility in the flushing media at FIGURE 7. Pressure buildup across the soil column during the flushing
experiments.
higher contamination levels.
Total HCB recovered from highly contaminated soil using were terminated after 12 pore volumes, and higher removal
natural surfactant solutions for 12 pore volumes was about could be achieved by continuing the flushing operations. This
200 g for 0.5% and about 1000 g for 1.0% natural surfactant. significantly higher removal of HCB with natural surfactant
These amounts are about 20 and 100 times more than that solutions is very encouraging because these solutions can
recovered with water (10 g) from soil columns contaminated possibly be used as a supplement at existing pump-and-treat
with 90 mg of HCB/kg of soil. The total HCB removed from facilities and to enhance the performance of the process.
the soil column as a percent of initial HCB in the column was HCB remaining in the soil column was determined by
about 0.02, 0.4, and 4% for water flood, 0.5%, and 1% natural slicing the column into four approximately equal sections
surfactant, respectively. It should be noted that experiments and analyzing each section independently in duplicate. The

674 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 31, NO. 3, 1997


removal of HCB was mainly from the influent end, and the Literature Cited
HCB present at the exit did not change appreciably. HCB
removal from the soil in one-dimensional soil flushing (1) Abdul, S. A.; Gibson, T. L.; Rai, D. N. Ground Water 1990, 28 (6),
920-926.
experiments starts at the influent end and progressively moves
(2) Edwards, D. A.; Luthy, R. G.; Liu, Z. Environ. Sci. Technol. 1991,
toward the effluent end. 25 (1), 127-133.
Figure 6a,b depicts the effect of surfactant concentration (3) Liu, Z.; Edwards, D. A.; Luthy, R. G. Water Res. 1992, 26 (10),
on the removal of HCB for natural surfactant solutions at two 1337-1345.
levels of soil contamination (2 and 90 mg of HCB/kg of soil). (4) Abdul, S. A.; Gibson, T. L.; Ang, C. C.; Smith, J. C.; Sobczynki, R.
It is clear that with an increase in the concentration of natural E. Ground Water 1992, 30 (2), 219-231.
(5) Liu, M. Mobilization of a Hydrophobic Organic Compound Using
surfactant there is a significant increase in the removal of Surfactant for Soil Washing. Ph.D. Dissertation, Louisiana State
HCB from the soil column. The higher removals with higher University, Baton Rouge, LA, 1993.
surfactant concentration can be explained by the increased (6) Fountain, J. C.; Klimek, A.; Beikirch, M. G.; Middleton, T. M. J.
solubility of HCB in the surfactant micelles. With the increase Hazard. Mater. 1991, 28, 295-311.
in surfactant concentration the number of micelles will (7) Kommalapati, R. R. Soil Flushing of Non Aqueous Phase Liquids
increase, resulting in an increased solubilization of HCB. The Using Conventional Surfactant Solutions and Colloidal Gas
Aphron Suspensions. M.S. Thesis, Louisiana State University,
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matrix. This suggests that micellar solubilization is the (8) Gannon, O. K.; Bibring, P.; Raney, K.; Ward, J. A.; Wilson, D. J.;
primary mechanism responsible for the mobilization and the Underwood, J. L.; Debelak, K. A. Sep. Sci. Technol. 1989, 24 (14),
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Hydrophobic Organic Compounds. M.S. Thesis, Louisiana State
the removal increased significantly. After 12 pore volumes University, Baton Rouge, LA, 1994.
using 0.5% solution, about 200 g of HCB was recovered as (10) Kommalapati, R. R. Remediation of Contaminated Soils Using
compared to 1000 g using a 1% solution and 3300 g in 11 Plant Based Surfactant. Ph.D. Dissertation, Louisiana State
pore volumes using a 2.5% solution. In contrast, the water University, Baton Rouge, LA, 1995.
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31 (10).
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increased to 60 psi in 3-4 pore volumes (not shown in the for the Examination of Water and Wastewater, 18th ed.; American
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interactions of surfactant molecules with soil minerals. 247-263.
However, the specific interactions that are responsible for (25) Nash, J. H. Field Studies of In-Situ Soil Washing; EPA/600/2-
the increase in pressure buildup are not well established at 87/110; United States Environmental Protection Agency: Cin-
cinnati, OH, 1987.
this time. From our studies, it appears that natural surfactant
at a concentration of 1% is a good compromise to achieve
higher removal and avoid high pressure buildup across the Received for review February 27, 1996. Revised manuscript
soil column. received October 15, 1996. Accepted October 23, 1996.X

Acknowledgments ES960181Y
This research was funded by the United States District Court,
Middle District of Louisiana, through the Louisiana State
University Hazardous Waste Research Center. X Abstract published in Advance ACS Abstracts, January 15, 1997.

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