Environ. Sci. Technol.

2003, 37, 3978-3984

A Novel Technique for Rapid

Extraction of Volatile Organohalogen
Compounds from Low Permeability
Media
IULIANA DINCUTOIU,
TADEUSZ GO
R E C K I , * , A N D
BETH L. PARKER
Departments of Chemistry and Earth Sciences,
University of Waterloo, 200 University Avenue West,
Waterloo, Ontario, N2L 3G1, Canada

A new method for rapid extraction of Volatile Organic

Compounds (VOC) from low permeability, unconsolidated
geologic media such as clayey soil has been developed and
tested using trichloroethylene (TCE) as the model
compound. The technique is based on a combination of
sonication and mechanical agitation of the samples. The
sample vials, mounted in a special holder attached to an
orbital shaker, were immersed in an ultrasonic bath during
extraction. The extracts were analyzed by gas chromatography with electron capture detection (GC-ECD). The
method was validated using clay samples from a TCEcontaminated industrial site by comparing TCE recoveries
to those obtained by the standard methanol extraction.
In all cases, the recoveries obtained with the new method
were the same or better than the recoveries obtained
with the reference method. The extraction time was shortened
from 5 days with the standard method to less than 2 h
with the new method. The new technique makes it possible
to analyze a large number of samples in a short time,
without the need for sample preservation and prolonged
storage. It has good potential for on-site analysis to facilitate
decisions while field investigations are in progress.

Introduction
Pollution of water, air, and soil with Volatile Organic
Compounds (VOCs) is considered a severe problem due to
the impact these compounds have on living organisms. Many
contaminated industrial sites exist across North America and
Europe where VOCs such as chlorinated solvents occur in
fine-grained geologic deposits. The need to conduct risk
assessments and develop remediation plans prompts investigations to determine the subsurface VOC distribution
in these clayey or silty soils. However, soil is one of the most
difficult matrices to analyze. The extent to which analytes
are attached to the matrix determines their recovery during
extraction. Among various types of soil, low permeability
clayey media are one of the most difficult to analyze because
of the matrix characteristics.
* Corresponding author phone: (519)888-4567 x 5374; fax: (519)746-0435; e-mail: tgorecki@uwaterloo.ca.
Presented in parts at Pittcon 2002, New Orleans, LA, March 1722, 2002 and Enviroanalysis 2002, Toronto, ON (Canada) May 27-30,
2002.
Department of Chemistry.
Department of Earth Sciences.
3978

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 17, 2003

The mineralogical composition, particle size, density, and

porosity are some of the important parameters to be
considered when VOCs are extracted from soil. The adsorption capacity of VOCs in soils is determined to a large extent
by the available surface area.1 It is also strongly related to the
diffusivity of a contaminant in soil.1,2 The adsorption capacity
determines the matrix capability to release the compound
during extraction. It varies with the water content of the soil
and aging as well as chemical and physical properties of the
soil.3,4 In a study of VOC sorption onto clay, sand, and
limestone, it was found that clay had the highest sorption
capacity.1 In the investigations reported in this paper, the
soil samples were obtained from a site where the VOC
contamination has been in the ground for a few decades.
This is common for most VOC contaminated field sites.
In permeable deposits such as sand or gravel, emphasis
in contaminated site investigations is placed on sampling
the groundwater using wells or other devices. In recent years
the use of mobile, on-site laboratories that conduct field
VOC analyses in groundwater has become common. Although
there is a similar need for field VOC analysis of clayey soil,
no suitable methods exist. The long time required to extract
VOCs from clay by the currently used methods is very
inconvenient (especially when a large number of analyses
must be performed) and renders field analysis for the
evaluation of the level of contamination practically impossible. Field analysis minimizes the time between sample
collection and analysis. This eliminates to a large extent the
problems related to contamination, losses, and/or degradation of the sample during transportation and storage. Onsite investigations produce immediate results, supporting
real-time decisions, interactive sampling, and cost-effective
solutions, especially when corrective measures are immediately required.
The goal of this study was to develop a method that would
produce results equivalent to those obtained by the method
currently in use but in a much shorter time. Because no
standards or reference materials were available for the
experiments, the only way to assess the performance of the
new method was to compare the results obtained by this
method for each individual sample to the results obtained
for the same samples after they were allowed to equilibrate
with the extracting solvent (methanol), as in the standard
procedure.

Background
Extraction of organic analytes from soils is still conducted
mostly by Soxhlet extraction and flask extraction. Both these
methods are time-consuming and require large amounts of
solvents.5-7 Soxhlet extraction is generally not suitable for
VOC extraction from soils, due to large VOC losses when
refluxing the solvent for the typical long extraction times of
this technique. Besides, further losses occur if concentration
of the extract is required. A number of new techniques for
the determination of organic compounds in solid matrices
have been developed recently; however, little attention has
been paid to extraction from low permeability media, such
as clay. Modern extraction techniques that can be useful in
the extraction of organics from soils include Pressurized
Liquid Extraction (PLE) (also called Accelerated Solvent
Extraction (ASE)), Supercritical Fluid Extraction (SFE), Microwave Assisted Extraction (MAE), headspace analysis (HS),
purge-and-trap (PT), ultrasonic extraction, and Solid-Phase
Microextraction (SPME). Many of these techniques proved
to be superior to Soxhlet extraction considering factors such
as solvent consumption, extraction time, and analyte recovery
10.1021/es0340275 CCC: $25.00

2003 American Chemical Society

Published on Web 08/06/2003

for soils with high to medium permeabilities.3,6,8-10

Both ASE and SFE yield good recoveries in a short time
for some semi- and nonvolatile organic compounds in soil
samples,7 but they are generally not well suited for VOC
determinations. In both techniques, losses of volatile analytes
might occur at the extract collection stage (hot solvent
discharge to a vented flask in ASE; supercritical fluid
decompression in SFE). The instrumentation is expensive,
and successful analyte recovery depends among others on
the type of soil.7-9 MAE is also used primarily for semi- and
nonvolatile analytes. It is less expensive than many of the
new methods. Nevertheless, the technique is not very popular.
One reason may be the fact that the effectiveness of MAE is
highly dependent on matrix characteristics.11 In all three
techniques, further VOC losses might occur if concentration
of the extract is required.
The most popular techniques for VOC analysis in soil
samples are static headspace and purge-and-trap.3 The latter
is recommended by U.S. Environmental Protection Agency
(U.S.-EPA) for volatile contaminants that have diffused onto
external surfaces but not into internal micropores of soil.9,12
Consequently, this method is not suitable for VOC analysis
in clay samples. Many previous studies have shown that hot
methanol extraction is more efficient than the approved
purge-and-trap and headspace techniques in terms of
accuracy regardless of the type and age of the contaminated
soil.12,13
Static headspace analysis requires a thermodynamic
equilibrium between the solid sample and the gas phase.
This equilibrium is usually difficult to achieve. High temperatures are required to increase the diffusivity and the
gas/solid distribution ratio of the volatile analytes, and that
may lead to analyte losses. In addition, quantitative calibration is very difficult in this method.14 Static headspace can
be used for matrices that behave as though the VOCs are
dissolved in the matrix, while soils represent an adsorption
system where the VOC distribution is determined by adsorption coefficients.14 Consequently, this method in its
typical implementation is not suitable for clay samples.
SPME is useful mainly for gaseous and liquid samples. It
relies on analyte equilibration between the sample and the
extracting device (SPME fiber). Thus, all factors affecting
equilibration must be controlled for accurate quantitative
analysis.15 Despite all the advantages of regular SPME in the
analysis of air and water samples, it has severe limitations
when it comes to quantitative analysis of soil samples,9
including the analysis of volatile compounds.14 Zhang and
Pawliszyn16 reported good recoveries of BTEX from spiked
clay samples with the use of an internally cooled SPME fiber,
but the device is not available commercially.
Solvent extraction is a very reliable method for VOC
evaluation in soil.13,17 Hewitt concluded that methanol
extraction is a more reliable method of recovering VOCs from
soil compared to methods based on vapor partitioning.13
Sonication extraction using focused high-intensity sound
waves is an enhanced solvent extraction technique. Vibrations
in the ultrasonic range create cavitation in the solvent and
the porous medium, resulting in high differential fluid
velocities. These velocity perturbations are capable of
overcoming the forces binding soil particles to each other
and clay microparticles to the soil matrix.18 In addition,
ultrasonic radiation generates heat, which further aids the
extraction process. Sonication improves mass transfer conditions and helps disintegrate larger particles. U.S.-EPA
recommends the use of sonication for the extraction of
nonvolatile and semivolatile organic compounds from soils.19
The instrumentation is simple and the cost is low.
To the best of our knowledge, few if any articles were
published with regard to VOC analysis in low permeability
media. Difficulties in measuring VOCs in soil are under

investigation by the U.S.-EPA. This paper presents the results

of our research on the development of a sonication extraction
method for the analysis of trichloroethylene (TCE) in natural
clayey samples. The analyte is a widely spread environmental
pollutant, found at many contaminated sites.

Experimental Section
Solvents and Standards. HPLC grade methanol (Fischer
Scientific) was used for TCE extraction from natural clayey
samples. HPLC grade hexane, 99+% purity (Sigma-Aldrich)
was used as exchange solvent for GC analysis. Sigma-Aldrich
1, 2-dibromoethane (DBE) of 99.5% purity, and BDH-assured
grade TCE of 99.5% purity were used for standards and solvent
preparation. Initially, DBE was used as internal standard for
GC injection. In further experiments, DBE was used as a
surrogate standard in methanol extraction to compensate
for possible losses during sample preparation and the entire
process of extraction and assessment of TCE recovery. DBE
concentration in the injection solvent, hexane, ranged from
500 to 550 ppb. DBE concentration in methanol was around
38.8 mg/L, so that in the injection solvent its concentration
was 500-550 ppb. Standards of TCE with DBE as internal
standard were prepared for eight levels of concentration,
starting with 1 ng/mL to 3 g/mL (final concentrations of
TCE in hexane).
Samples. Soil samples were collected from an inactive
industrial site in Kitchener, Ontario, where TCE has existed
in the subsurface for at least 20 years.20 The TCE occurs in
various geologic layers, from which a silty clay layer was
selected to obtain the core samples for this study. Care was
taken to collect the samples from the same location, at a
depth of about 5 m. The clayey layer is classified geologically
as a glacial till, which is a common type of deposit in the
glaciated interior region of North America. This layer is
comprised mineralogically of quartz, feldspars, carbonate
minerals, and nonswelling clay minerals, primarily illite. The
layer occurs below the water table and, therefore, under field
conditions, is water saturated. The wet and dry bulk densities
are 2.24 and 1.96 g/cm3, respectively, solid density of 2.88
g/cm3, porosity of 0.3, and fractional organic carbon of 0.24%
dry weight basis.20
Standard Procedure. The standard method used in our
laboratory for the determination of VOC concentrations in
low permeability soils was described by Parker.21 In this
method, concentrations are determined on small subsamples
from cores using methanolic extraction. Only a brief description is provided here. The core segments were collected
using equipment described by Zapico et al.22 A core barrel
(1.52 m length) was driven into the ground using a pneumatic
hammer. While the barrel was driven, the soil core entered
an aluminum tube (5.1 cm outside diameter) held inside the
barrel. Inside the tube, a piston connected by wire-line to
surface maintained suction to prevent soil from falling out,
ensuring complete recovery and retention of pore water.
Immediately after raising the coring system from the ground,
the aluminum tube containing the core was removed from
the barrel and Teflon caps were placed on the ends, followed
by preservation at 4 C. At the time of subsampling for VOCs,
the core tube was split longitudinally and stainless steel
subcoring devices were used to collect samples of around
6-10 g, which were placed in 25 mL vials with screw caps
and Tegrabond septa. The subsampling procedure was done
fast and care was taken to wrap the two pieces of the core
in aluminum foil in order to avoid significant losses of the
analyte(s). Each vial was weighed before and after collection
of the clay sample. Twenty milliliters of HPLC grade methanol
(MeOH) were added to each vial, which was then agitated
vigorously for 1 min using a standard Mini-vortex stirrer
(VWR) and for another 30 min on an orbital shaker model
3520 (Lab-Line Instruments, Inc., Melrose Park, IL) at 300
VOL. 37, NO. 17, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

3979

TABLE 1. TCE Concentration in Diluted Clay Extracts Obtained

by the Standard Method Currently in Use in the Laboratory
TCE concn
TCE concn
after shaking after 5 days % increase average
sample
(ng/mL)
(ng/mL)
after 5 days increase% RSD%

FIGURE 1. Schematic diagram of the device for simultaneous

shaking/sonication.
rpm. Samples prepared in this way were allowed to equilibrate
for 5 days, following which they were centrifuged for 30 min
with an IEC CRU-5000 centrifuge (Damon/IEC Division) at
1700-1800 rpm. Samples for final analysis by gas chromatography were prepared by adding 20 L of the MeOH extract
to 1.5 mL of hexane containing DBE as the internal standard.
Methanol was the extraction solvent of choice because it
efficiently penetrates the intraparticle regions, which results
in an increase in solute diffusivity and allows a reasonable
detection limit to be achieved. Since methanol is very polar,
it is incompatible with the nonpolar GC column stationary
phase used in the final determination of VOC. Thus, solvent
exchange was required before the extract was injected into
the GC. Analyses were performed on an HP6890 GC equipped
with a -ECD detector and a capillary fused silica column,
30 m 530 m 3.0 m DB-624 (J&W). The carrier gas,
helium (Ultrahigh Purity, Praxair), was set to a constant flow
of 8.1 mL/min. The injection was performed in pulsed splitless
mode. An aliquot of 1 L of the liquid sample was injected
using the autoinjector. The injector temperature was set to
225 C, the column was kept for 3 min at 55C, followed by
an increase to 105 C at a rate of 30 C/min. At this
temperature the column was held for 2 more min. The
detector was operated at 300 C using nitrogen (ECD grade,
Praxair) as the makeup gas at a flow rate of 60 mL/min.
The limit of detection for the method is 0.15 mg/kg soil
(w.w.) for a 10 g soil sample. The linear working range of the
method is 0.45-450 mg/kg soil. It can be extended to higher
concentrations by spiking the hexane with a smaller volume
of the methanolic extract or by diluting the extract. On the
other hand, the limit of detection of the method can be
improved by a factor of 76 (down to 2 g/kg) by elimination
of the solvent exchange step. This can be achieved by using
direct cool on-column injection of the methanolic extract to
the GC column.23
Sonication. A CREST TRU-SWEEP sonicator model 275D
was used, featuring digital control of heat, time, and power.
The TRU-SWEEP technology ensures uniform distribution
of the ultrasound energy in the sonicating bath by eliminating
standing waves and the resultant hot spots. The power
level was set at maximum (corresponding to 90W sonic
power), and the frequency of the ultrasound radiation was
38.5 kHz. Since the bath tended to overheat slightly during
prolonged sonication, water circulation was introduced by
slowly adding cold running water to the bottom of the bath
and draining warm water from the top.
For the experiments involving sonication followed by
mechanical agitation, the procedure consisted of initial
mechanical agitation of the samples (as in the standard
procedure), followed by sonication at 45 C for 0.5 h and
mechanical agitation for an additional 0.5 h.
A special device was developed to allow simultaneous
sonication and mechanical agitation of the samples. The
design of the device is illustrated in Figure 1. An aluminum
plate equipped with three vertical aluminum rods, each
provided with two clamps to hold the vials, was connected
3980

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 17, 2003

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

584
1142
536
986
27
56
19
43
27
56
39
55
111
111
112
77
114
53
274

676
1497
702
1217
47
80
30
56
47
80
60
71
138
168
173
106
161
92
372

15.8
31.1
31.0
23.4
74.1
42.9
57.9
30.2
74.1
42.9
53.8
29.1
24.3
51.4
54.5
37.7
41.2
73.6
35.8

43.4

17.6

to an orbital shaker. The entire assembly was positioned

next to the ultrasonic bath, so that the vials could be immersed
in the bath while being shaken at the same time.
In the two-step procedure, the initial mechanical agitation
of the samples (as in the standard procedure) was followed
by simultaneous shaking (330 rpm) and sonication at 45 C.
Three different sonication extraction times were examined:
0.5 h, 1 h, and 1.5 h. The one-step procedure was a shortened
version of the two-step procedure, in which the initial
mechanical agitation step was eliminated. Extraction times
of 1 and 1.5 h were examined.
In all cases, the sample size, solvent volume, and the postextraction procedure were identical to the ones used in the
standard method. Consequently, the limits of detection and
the working range were also the same.

Results and Discussion

Organic contaminants in aged clay samples can be found
throughout the bulk of the material, which indicates that
they enter the micropores in clay. Since transport in the
micropores is mostly via molecular diffusion, a very slow
process, it is highly desirable to make the diffusion distances
during extraction as short as possible. This is typically
accomplished by vigorous agitation of the samples, which
leads to disintegration of the clay subcores into smaller
aggregates. However, the time required to accomplish
complete disintegration of all clay particle aggregates can be
very long, which creates a bottleneck in the sample preparation process. We propose to achieve the same goal in a much
shorter time by combining mechanical agitation with sonication. The latter delivers additional energy to the sample,
promoting disintegration of small aggregates as a result of
cavitation and enhancing solvent penetration of the micropores.
Development of a Spiking Procedure. Spiked samples
are usually used in the development of new extraction
techniques. To be useful in the study, spiked clay samples
would have to mimic natural contaminated clay as much as
possible. Apart from having known and controlled total
analyte concentration in the sample, analyte distribution
throughout the spiked subcore would have to be uniform.
Besides, it would have to be demonstrated that spiked
samples behave in the same way as the naturally aged native
samples. Several different approaches to spiking, usually
incorporating an aging period, were tried. While it was

TABLE 2. TCE Concentration in Diluted Clay Extracts Obtained by Sonication Extraction Followed by Shaking and 5 Days of
Equilibration

sample
1
2
3
4
5
6
7
8

extraction
time, h
0.5

TCE concn
after
shaking
(ng/mL)

TCE concn
after 5
equilibration
days (ng/mL)

concn
difference
(ng/mL)

relative
difference
%

220
161
52
196
146
153
113
231

223
161
51
190
137
143
100
215

3
0
-1
-6
-9
-10
-13
-16

1.35
0.00
-1.96
-3.16
-6.57
-6.99
-13.00
-7.44

possible to produce spiked samples with uniform analyte

distribution that produced extraction time profiles similar
to those of the native samples, analyte recoveries from the
spiked samples were never quantitative and varied widely
due to losses incurred at the different stages of spike
preparation. Consequently, this approach was abandoned
in favor of using real samples from a contaminated site.
Solvent Extraction using the Standard Method. Initial
experiments were performed using the standard solvent
extraction procedure (see Experimental Section) to establish
a reference for further experiments. The main goal was to
find the average increase in TCE concentration during the
equilibration period of 5 days. A series of experiments was
conducted on 19 clay samples that were analyzed according
to the standard procedure. The extracts were analyzed
immediately following the 30 min agitation on the orbital
shaker and after 5 days of equilibration with methanol. The
results are presented in Table 1. The average increase in TCE
concentration in the extract over the period of 5 days of
equilibration was 43.4%, with a standard deviation of 17.6%.
Sonication Extraction. Early experimental procedure was
based on the standard method of VOC extraction from clay
for the primary stage of core and sample collection and
placement into vials containing methanol for preservation
and extraction. The difference was that after shaking on the
orbital shaker, the vials with clay samples were sonicated at
a constant temperature of 45 C. Different sonication times
were investigated, from 0.5 h to 8 h. At every 0.5 h interval,
aliquots of the extract were collected and analyzed in order
to determine the extraction time profile of TCE from clay.
The results demonstrated no need for sonication for more
than 1.5 h, as no further increase in TCE concentration in
the extracts was observed after this time. Moreover, during
the 8 h experiment, a decrease in analyte concentration
ranging from 1.8 to 7.5% was observed. Consequently, the
remaining experiments were conducted only for three time
intervals: 0.5 h, 1 h, and 1.5 h.
TCE loss during prolonged sonication could have been
caused by analyte decomposition; however, it seemed more
plausible that the loss was caused by sorption into the septum
material (PTFE-lined poly(dimethylsiloxane)), especially following collection of the aliquots of the extract when the PTFE
lining was pierced. The latter possibility was evaluated using
standard solutions of about 23 g/mL TCE in methanol. The
solutions were stored for 2.5 h at 45 C, and the observed
analyte losses ranged from 1.1% to 4.3%, close to the values
observed for the sonicated samples. Thus, it was assumed
that analyte decomposition did not occur during prolonged
sonication and that the losses were due to sorption.
Compared to the TCE concentration in MeOH immediately after agitation of the sample vials on the orbital
shaker, an increase in concentration ranging from 2.0 to 13.1%
was observed after the sonication of the clay samples.
However, an additional increase in TCE concentration by

average
relative
difference
%
-4.72

SD

calculated
Students t
(absolute
value)

critical
Students
t

4.69

2.851

2.306

8.6-53.8% was observed after the 5 days of equilibration

following the sonication. The increase was statistically
significant at 95% probability level. Thus, it was clear that
while sonication may have increased the rate of extraction
somewhat, it did not yield complete analyte recovery in a
short time, the stated goal of this study. Visual examination
of the samples revealed that the clay particles settled very
rapidly at the bottom of the vials during sonication. Apparently, the additional energy introduced to the system helped
overcome repulsive forces between clay particles, promoting
their settling. The layer of clay found at the bottom of the
vials immediately after sonication, typically stratified according to the particle size, was usually much more compacted than the layers formed in vials that were only
mechanically shaken and allowed to settle over 5 days. In
fact, very vigorous shaking was required to resuspend the
particles that settled at the bottom of the sonicated vials.
Thus, while sonication accelerated the disintegration of clay
particle aggregates, it also promoted the settling of the
particles, leading to the formation of a very compact layer
of clay at the bottom of the vials. Transport of the analyte
molecules by molecular diffusion was most likely very slow
in these layers. Formation of low permeability layers in clayey
soils subjected to sonication was also observed in the study
of Reddi et al.18
Sonication Followed by Mechanical Agitation. Keeping
the disintegrated clay particles in suspension seemed vital
in order to achieve complete analyte recovery in a short time.
Reddi et al.18 observed that subsonic vibrations following
ultrasonic excitation mobilized additional clay fines. It was
decided therefore to resuspend the tight clay layer formed
at the bottom of the vials after sonication by vigorous shaking
of the vials for 30 min using the orbital shaker (see
Experimental Section). Once the particles were dispersed
again in the solvent, the diffusion distances were reduced,
and the extraction process was accelerated as a result.
Because no standards or reference materials were available
for the experiments, the only way to assess the performance
of the new method was to compare the results obtained by
this method for each individual sample to the results obtained
for the same samples after they were allowed to equilibrate
for 5 additional days with the extracting solvent (MeOH), as
in the standard procedure. The two sets of results were
compared using Students t-test for the individual differences.24 The zero hypothesis was that the two methods
produced identical results, and the differences were caused
by random factors only, while the alternative hypothesis
stated that the differences were caused by systematic factors.
Because analyte levels in the natural samples varied widely,
we chose to compare percent relative differences rather than
absolute differences.
The results for this version of the technique are presented
in Table 2. Since the average difference had a negative sign,
we compared the absolute value of tcalc with the value of tc
VOL. 37, NO. 17, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

3981

TABLE 3. TCE Concentration in Diluted Clay Extracts Obtained for the Two-Step Simultaneous Sonication and Shaking Procedure,
for Three Time Intervals and after Five Equilibration days

sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54

extraction
time, h
0.5

1.5

TCE concn
after
sonication
(ng/mL)

TCE concn
after 5
equilibration
days (ng/mL)

concn
difference
(ng/mL)

relative
difference
%

1485
700
1189
1316
1414
1669
1584
1338
1615
497
956
1286
1325
1585
1069
595
1018
763
1064
1655
1177
773
465
91
73
39
111
75
457
745
554
1133
380
787
1071
807
1709
1542
608
729
1639
1598
633
1564
25
34
92
49
38
65
43
38
25
53

1478
695
1178
1301
1415
1676
1603
1345
1642
503
957
1261
1306
1561
1041
605
1074
811
1118
1752
1289
792
478
89
72
37
128
78
463
746
552
1131
383
788
1063
805
1742
1589
633
756
1603
1613
656
1602
25
34
90
48
41
64
43
39
24
53

-7
-5
-11
-15
1
7
19
7
27
6
1
-25
-19
-24
-28
10
56
48
54
97
112
19
13
-2
-1
-2
17
3
6
1
-2
-2
3
1
-8
-2
33
47
25
27
-36
15
23
38
0
0
-2
-1
3
-1
0
1
-1
0

-0.5
-0.7
-0.9
-1.2
0.1
0.4
1.2
0.5
1.6
1.2
0.1
-2.0
-1.5
-1.5
-2.7
1.7
5.2
5.9
4.8
5.5
8.7
2.4
2.7
-2.2
-1.4
-5.4
13.3
3.8
1.3
0.1
-0.4
-0.2
0.8
0.1
-0.8
-0.2
1.9
3.0
3.9
3.6
-2.2
0.9
3.5
2.4
0.0
0.0
-2.2
-2.1
7.3
-1.6
0.0
2.6
-4.2
0.0

at the 95% probability level. We found that |tcalc| > tc(95%);

therefore, we had to conclude that the two sets of results
differed statistically significantly at the chosen probability
level. The decrease in concentration observed for nearly all
samples after they were equilibrated with methanol for the
additional 5 days, albeit small, could not be explained by
random factors only. This does not mean, however, that the
method developed did not yield good results. On the contrary,
it seems that complete or nearly complete analyte recovery
was achieved in the short time required for the new
procedure, following which analyte losses (e.g. through
sorption) could only occur during further equilibration.
3982

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 17, 2003

average
relative
difference
%
1.40

SD

calculated
Students
t

critical
Students
t

3.87

1.916

2.049

0.67

1.89

1.589

2.086

0.69

3.93

0.432

2.447

The method proposed involved a three-step procedure

(shaking-sonication-shaking), which we considered cumbersome. In addition, it would be advantageous to further
shorten the sample preparation time. Consequently, we
decided to combine shaking and sonication into a single
step.
Simultaneous Shaking and Sonication - Two-Step
Procedure. Initial processing of the samples was kept
unchanged. The samples were shaken for 30 min on the
orbital shaker, following which they were placed in the device
allowing simultaneous sonication and agitation (see Figure
1). Initially, the vials were mounted vertically during pro-

TABLE 4. TCE Concentration in Clay Extracts Obtained for the One-Step Simultaneous Shaking and Sonication Extraction

sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

extraction
time, h
1

1.5

TCE concn
after
sonication
(ng/mL)

TCE concn
after 5
equilibration
days (ng/mL)

concn
difference
(ng/mL)

relative
difference
%

845
842
817
953
802
282
687
757
147
490
921
923
801
375
595

847
837
812
948
797
283
683
757
146
487
949
918
798
376
596

2
-5
-5
-5
-5
1
-4
0
-1
-3
28
-5
-3
1
1

0.2
-0.6
-0.6
-0.5
-0.6
0.4
-0.6
0.0
-0.7
-0.6
3.0
-0.5
-0.4
0.3
0.2

cessing. The observed increase in TCE concentration varied

from 26.4 to 45.1% during sonication, and further 3.8-20.9%
after the 5 additional days of equilibration following sonication. The average initial increase in TCE concentration
was higher than that observed in the experiments involving
sonication only (see above), but complete analyte recovery
was not achieved during sonication. Visual examination of
the vials indicated that clay particles still tended to settle at
the bottom (although to a lesser extent), despite the mechanical agitation. Apparently, the circular motion of the
orbital shaker combined with the circular cross-section of
the vials did not provide enough agitation. To alleviate this
problem, we changed the position of the vials immersed in
the sonication bath from vertical to horizontal (the position
in which the vials are normally agitated on the orbital shaker).
The results of these experiments, summarized in Table 3,
proved that this approach achieved the stated goal. The
change in TCE concentration after 5 days of equilibration
following the combined agitation/sonication was negligibly
small, with both positive and negative signs. A total of 54 clay
samples were investigated for three different extraction times.
The samples were analyzed immediately after sonication and
after 5 additional days of equilibration. The tcalc values
calculated for the differences between the resultant pairs of
results were lower than the tc at the 95.0% probability level
for all three extraction times. For the 28 samples investigated
at 0.5 h extraction time, the interpolated tc value was 2.049,
while tcalc was 1.916. For 1 h extraction, tcalc ) 1.589 (n ) 24)
compared to tc ) 2.086. Similarly, for the six samples sonicated
for 1.5h, tcalc ) 0.432, while the critical value was 2.447. Since
in all cases tcalc values were lower than the critical values, it
can be concluded that the two methods did not differ
significantly at the 95% probability level, and the differences
between the results obtained using the two methods could
be explained by random factors.
This approach to extraction of TCE from clay samples
yielded the same results as the standard methanol extraction
method, but in a much shorter time (less than 2 h compared
to 5 days). This indicates that the method has a very good
potential in the analysis of VOCs in clay, especially when the
results have to be produced fast (e.g. in field analysis).
Simultaneous Shaking and Sonication - One-Step
Procedure. The one-step procedure was a shortened version
of the two-step procedure described above, in which initial
processing of the samples (30 min agitation using an orbital
shaker) was eliminated. Table 4 summarizes the results of
the experiments. Changes in TCE concentration in the
extracts after 5 days were negligibly small, with both negative

average
relative
difference
%

SD

calculated
students
t

critical
Students
t

-0.34

0.435

2.056

2.365

0.15

1.191

0.345

2.306

and positive signs. Seven clay samples were investigated for

the 1 h extraction time and eight clay samples for the 1.5 h
extraction time. Analyses were performed immediately after
the extraction and after 5 equilibration days.
From Table 4, the tcalc values for the two extraction periods
were lower than the tc values at the 95% probability level. For
the seven samples investigated at 1 h extraction time, tcalc
was 2.056, while the critical value tc was 2.365. For the eight
sample series investigated at 1.5 h extraction time, the tcalc
was 0.345, while tc was 2.306. It can be concluded, therefore,
that the two methods did not differ significantly at the 95%
confidence level, and random factors could explain the
differences between the results.
Similarly to the two-step procedure, the one-step procedure yielded excellent results in a very short time, with
minimum sample manipulation. The clear advantages of
performing TCE extraction by combining shaking with
sonication without initial sample processing make this
technique very attractive for VOC analysis in low permeability
media including clay, especially in the field when results are
required in near real-time. The number of samples that can
be processed in a single batch by this method can be easily
increased by using a larger ultrasonic bath.

Acknowledgments
We express our gratitude to CRESTech, NSERC and the
University of Waterloo Consortium Solvents-in-Groundwater
Research Program for the financial support of this study.

Literature Cited
(1) Ruiz, J.; Bilbao, R.; Murillo, M. Environ. Sci. Technol. 1998, 32,
1079.
(2) Petersen, L. W.; Rolston, D. E.; Moldrup, P.; Yamaguchi, T. J.
Environ. Qual. 1994, 23, 799.
(3) Ojala, M.; Mattila, I.; Tarkiainen, V.; Sarme, T.; Ketola, R. A.;
Maattanen, A.; Kostiainen, R.; Kotiaho, T. Anal. Chem. 2001, 73,
3624.
(4) Petersen, L. W.; Moldrup, P.; El-Farhan, Y. H.; Jacobsen, O. H.;
Yamaguchi, T.; Rolston, D. E. J. Environ. Qual. 1995, 24, 752.
(5) Dean, J. R.; Xiong, G. Trends Anal. Chem. 2000, 19, 553.
(6) Mingelgrin, U.; Gerstl, Z. J. Environ. Qual. 1983, 12, 1.
(7) Camel, V. Trends Anal. Chem. 2000, 19, 229.
(8) Heemken, O. P.; Theobald, N.; Wenclawiak, B. W. Anal. Chem.
1997, 69, 2171.
(9) Clement, R. E.; Yang, P. W.; Koester, C. J. Anal. Chem. 2001, 73,
2761.
(10) Llompart, M. P.; Lorenzo, R. A.; Cela, R.; Li, K.; Belanger, J. M.
R.; Pare, J. R. J. J. Chromatogr. A 1997, 774, 243.
(11) Zlotorzynski, A. Crit. Rev. in Anal. Chem. 1995, 25, 43.
VOL. 37, NO. 17, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

3983

(12) Askari, M. D. F.; Maskarinec, M. P.; Smith, S. M.; Beam, P. M.;

Travis, C. C. Anal. Chem. 1996, 68, 3431.
(13) Hewitt, A. D. Environ. Sci. Technol. 1998, 32, 143.
(14) Kuran, P.; Sojak, L. J. Chromatogr. A 1996, 733, 119.
(15) Nilsson, T.; Montanarella, L.; Baglio, D.; Tilio, R.; Bidoglio, G.;
Facchetti, S. Int. J. Environ. Anal. Chem. 1998, 69, 217.
(16) Zhang, Z.; Pawliszyn, J. Anal. Chem. 1995, 67, 34.
(17) Minnich, M. M.; Schumacher, B. A.; Zimmerman, J. H. J. Soil
Contam. 1997, 6, 187.
(18) Reddi, L. N.; Hadim, A.; Prabhushankar, R. N.; Shah, F. J. Environ.
Eng. 1994, 120, 1544.
(19) Babic, S.; Petrovic, M.; Kastelan-Macan, M. J. Chromatogr. A
1998, 823, 3.
(20) Nowak, W. Age Determination of a TCE Source Zone Using
Solute Transport Profiles in an Underlying Clayey Aquitard;
Master Thesis, University of Waterloo, Canada, University of
Stuttgart, Germany, 2000.

3984

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 17, 2003

(21) Parker, B. L. Effects of Molecular Diffusion on the Persistence

of Dense, Immiscible Phase Organic Liquids in Fractured Porous
Geologic Media; Ph.D. Thesis, University of Waterloo, Canada,
1996.
(22) Zapico, M. M.; Vales, S. E.; Cherry, J. A. Ground Water Monit.
Rev. 1987, 7, 74.
(23) Gorecka, M.; Gorecki, T.; Parker, B. L.; 24th International
Symposium on Capillary Chromatography and Electrophoresis;
Las Vegas, Nevada, May 20-24, 2001.
(24) Harris, D. C. Quantitative Chemical Analysis, 5th ed.; W. H.
Freeman and Company: New York, 1998.

Received for review January 9, 2003. Revised manuscript

received April 9, 2003. Accepted April 24, 2003.
ES0340275