Groundwater Issue How Heat Can Enhance In-Situ Soil And Aquifer Remediation Important Chemical Properties And Guidance On Choosing The Appropriate Technique

                        United States
                        Environmental Protection
                        Agency
Office of
Research and
Development
Office of Solid Waste
and Emergency
Response
EPA/540/S-97/502 V/
April 1997
&EPA      Ground  Water  Issue
                        How Heat Can  Enhance In-situ Soil and Aquifer Remediation:
                        Important Chemical Properties and Guidance on
                        Choosing the Appropriate Technique
                        Eva L. Davis *
Background

The EPA Regional Ground Water Forum is a group of EPA
professionals representing Regional Superfund and Resource
Conservation and Recovery Act (RCRA) Offices, committed to
the identification and resolution of ground-water issues impact-
ing the remediation of Superfund and RCRA sites. Innovative
technologies for subsurface remediation, including in-situ tech-
niques based on heating the subsurface to enhance the recovery
of organic contaminants, are  being evaluated more often for
specific sites as the limitations to the conventionally-used tech-
niques are recognized. The purpose of this Issue Paper and the
three companion Issue Papers (Davis, 1997a, b, c) is to provide
to those involved in assessing remediation technologies some
basic information on the thermal remediation techniques.  In
order to understand how heat can  enhance a remediation
process, it is essential to understand the properties of organic
contaminants that affect their recovery. Thus, this Issue Paper
contains in-depth information on the properties of some common
organic contaminants which can affect their movement in and
recovery from the subsurface, as well as information on how
these properties are affected by temperature. Then, some basic
information on which of the heat-based remediation techniques
may be most appropriate for the subsurface conditions and the
contaminants is also provided, as well as a comparison of the
heat-based techniques to other in-situ remediation techniques.
The three companion Issue Papers have been written to provide
an explanation  of how each of the three general  types of
processes (steam or hot air injection, electrical heating, and hot
water injection) works, as well as preliminary information on the
design of a system and some estimates of the expected costs.
     Thus, once the ground-water remediation specialist has deter-
     mined which of the thermal methods may be appropriate for a
     particular site, the Issue Paper on that method may be consulted
     for more detailed  information  on how the process  may be
     applied.

     Introduction

     Thermal treatment is a common arid proven technology for the
     remediation of contaminated soils (Lighty et al., 1990), but in the
     past thermal treatment has been applied mainly to soils that have
     been excavated and are then incinerated to release and/or
     destroy the contaminants.  However, excavation of contami-
     nated soils is not always practical and can be extremely costly
     when the contamination occurs  at great depths or covers a large
     area. Excavation also increases the risk of exposure to and
     further dispersion of the contaminants during material handling
     steps (Dev et al., 1989; Superfund Report, August 10, 1994).
     Heat-based in-situ remediation methods can be used in many
     places where excavation is not possible,  such as under and
     around surface  structures,  and  around empty  underground
     tanks and utilities (U.S. EPA, 1995d). In many instances, heat-
     based in-situ remediation techniques have been found to be cost
     effective compared to the excavation and incineration option or
     other remediation techniques  (Dev et  al., 1989; Basile and
     Smith, 1994; Yow et al., 1995).
     * National Risk Management Research Laboratory, U.S. EPA
                       Superfund Technology Support Center for Ground Water

                       National Risk Management Research Laboratory
                       Subsurface Protection and Remediation Division
                       Robert S. Kerr Environmental Research Center
                       Ada, Oklahoma
                                    U.S. Environmental Protection Agency
                                   Printed on Recycled Paper

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The most commonly used remediation technique for the recov-
ery of organic contaminants from ground water has been pump-
and-treat, which recovers contaminants dissolved in the aque-
ous phase.  Vacuum extraction  (also called soil venting) is
quickly becoming popular for removal of volatile organic con-
taminants from the unsaturated zone in the gaseous phase (Ho
and Udell, 1992; Shah et al., 1995). Both of these techniques
can, in the initial remediation phase, rapidly recover contami-
nants at concentrations approximately equal to the solubility limit
(pump-and-treat), or the maximum gas phase concentration of
the contaminant (vacuum extraction). The maximum gas phase
concentration will depend on whether the contaminant is present
as a free phase or as a solute in the aqueous phase. During this
initial phase, large amounts of the contaminants may be re-
moved.  The second phase of the remediation, however, is
characterized by rapidly declining contaminant concentration in
the effluent as the rate of mass transfer into the flowing phase
controls the rate of removal.  The third phase of the remediation
is characterized by a tailing in the effluent of low contaminant
concentrations.  However, low effluent concentrations may not
be a reliable indication of low contaminant levels remaining in the
subsurface.  Diffusion of contaminants from less-permeable
areas into the regions where flow is occurring or the  slow
desorption of contaminants from the soil surface may control
contaminant  removal during this phase, and termination of the
extraction process before these processes  are complete may
lead to significant rebounding of the ground water and/or soil air
concentrations (Mackay and Cherry, 1989).

Thus, the rate-limiting properties of the systems are different in
each of the three phases of the remediation: in the first phase,
the solubility of the contaminant in the aqueous phase (pump-
and-treat) or its  maximum gas phase concentration (vacuum
extraction); in the second phase, it is the mass transfer step, i.e,
dissolution into the aqueous phase (pump-and-treat), or vapor-
ization  (vacuum  extraction); and,  during the third phase, it is
diffusion from  low permeability areas or the desorption rate
(Shahetal.,  1995).

Instances of soil and aquifer contamination by oily contaminants
such as automatic transmission fluid (Abdul et al., 1990), coal tar
(Gerencher et al., 1992) and creosote (Johnson,  1994)  have
been documented. Contaminants such as these oils are prac-
tically insoluble in water and have essentially no vapor pressure.
Thus, they will be present in the subsurface as a nonaqueous
phase liquid  and must be recovered as such.  The recovery of
these types of products  is often limited  by  slow movement to
recovery wells caused by their high viscosity and the significant
residual saturation left behind.  Heat-based in-situ remediation
techniques which overcome or lessen the influence of each of
these limitations to the recovery of organic contaminants have
been developed and are being field tested.

Properties of the Contaminants

Organic contaminants in the subsurface can be present as a
separate nonaqueous phase liquid, dissolved in the aqueous
phase, in the vapor phase in the soil gas, partitioned into the soil
organic matter, or adsorbed onto the solid mineral phase. The
relative amount of the contaminant in each of these phases is
determined largely by the properties of the contaminant. Gen-
erally, the most important property of the soil in determining the
distribution  of contaminants is the soil organic matter, which
normally controls the absorption of hydrophobic compounds.

Table 1 lists some of the relevant physical properties of volatile
and semivolatile organic chemicals that have been, or have the
potential  to be, recovered using in-situ  thermal  techniques.
Many of these are commonly found at Superf und sites and other
sites where ground-water contamination has occurred (Roberts
etal., 1982; Esposito et al., 1989; Newell etal., 1995). All of the
properties listed are temperature dependent.  Most of these
organics  are  essentially immiscible with  water; acetone and
methanol are the exceptions.  Many of these compounds have
low viscosities and, thus, have the potential to flow readily in the
liquid phase.  Approximately half of these compounds are less
dense than water; the other half are more dense than water. The
density of an organic liquid relative to that of water is important
in determining the vertical mobility of the contaminant.  Those
that are less dense than water will tend to float on the ground-
water table, while those that are more  dense than water may
move downward through the aquifer if the pressure in the organic
liquid is greater than the displacement  pressure of the aquifer
materials.  Low permeability clay layers in the aquifer may
restrict the vertical movement and allow the liquids to accumu-
late on top of the layer.

Table 1 is set up to  list  the chemicals in the order of lowest to
highest boiling  points.   Observation of the vapor pressures
shows that, in general, the lower the boiling point the higher the
vapor pressure at 25°C. The contaminants with the  lowest
boiling points  also generally have a lower heat of vaporization,
thus these contaminants are relatively easy to volatilize. Com-
pounds with higher boiling points have lower vapor pressures at
ambient temperatures and a higher heat of vaporization, thus
more energy is required to convert them to the gaseous phase.
Laboratory  experiments have shown that vaporization of even
highly volatile compounds can cause a measurable decrease in
the temperature of the system (Lingineni and Dhir, 1992).

Henry's law constants indicate whether the compound prefers to
be in the gaseous or aqueous state. Henry's law applies to dilute
solutions, and can be written as: PA = XAHc, where PA is the partial
pressure of chemical A, XA is the mole fraction of chemical A in
solution, and Hc is a  constant, commonly called the Henry's law
constant. Thus, the  Henry's law constants are a function of the
aqueous solubility and vapor pressure of a compound, and the
greater the Henry's law constant, the greater the extent to which
the compound partitions to the air phase (Atkins, 1986). The
constants given in the table are expressed in the dimensionless
form, which is a ratio of the concentrations, GJGvatel, where both
concentrations are  in mol/m3.  Due to difficulties involved in
determining solubilities and vapor pressures, reported values of
Henry's law constants sometimes vary by two orders of magni-
tude or more depending on the source of the data.  Mackay and
Shiu (1981) performed a critical review of the available data, and
determined recommended values for many chemicals of envi-
ronmental interest,  and a standard deviation of the  reported

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Table 1. Properties of some organic chemicals that have been found at contaminated sites.
Organic
Contaminant



Methylene
Chloride
(Dichloro-
methane)
1,2-Dichloro-
ethylene (trans)
Acetone
1 , 1 -Dichloro-
ethane
1,2-Dichloro-
ethylene (cis)
Trichloro-
methane
(Chloroform)
1 -Hexene
Methanol


n-Hexane
1,1,1-Tri-
chloroethane

Boiling Density
Point gm/cm3
°C


40 1.3182
25°C


49 1.2444
56.3 0.7899
57.4 1.17
60 1.2649
25°C
61.2 1.49

63.5 0.675
64.6 0.791


68.7 0.659
74.1 1.3303
25°C

Viscosity
cP
25°C


0.413



0.317
0.306
0.464
0.445
0.537

0.252
0.544


0.300
0.793

Water
Solubility
mg/1


20,000
20°Ce


600
20°CC
00
5500
20°CC
800
20°Ce
8000
20°Ce

50
20°Ce
00


9.5
20°Ce
4400
20°C

Vapor
Pressure
mmHg
T,,°C

260.9
10°C


198.7
10°C
121.7
10°C
125.8
10°C
104.8
10°C
98.6
10°C

90.0
10°C
58.5
10°C

80.8
10°C
67.4
10°C

Vapor
Pressure
mmHg
T2, °C

>760
50°C


>760
50°C
622.4
50°C
608.6
50°C
580.0
50°C
541.3
50°C

485.3
50°C
400
50°C

407.5
50°C
360.1
50°C

Henry's Law Octanol- Diffusion
Constant Water Coefficient
dimensionless Partition in Water
25°C Coefficient cirrVday

0.1 05 ±0.008" 17.78"




0.000842" 1.74" 1.106b*h
25°C
0.234 ± 0.008" 30"
61.7'

0.153 ±0.012" 90"
79.4'
93.3b
16.87 ±0.40" 2455'-"
0.151- 1.11°15°C
0.219 1.6S25°C
1.43h25°C
68.6 ±10.1" 10,000"
12,883r
1.13 ±0.016° 309b
300"
147.9'
Diffusion Heat of
Coefficient Vaporiz-
in Air ationb
cm2/day kJ/mol
25°C
28.82




9417.6s 30.99
0°C
30.62

7862s 31.28
0°C

6212h 30.61
20°C
14,6888 37.43


6143" 31.56
20°C
32.50

                                                                               Continued on next page.

-------
Table 1 - Continued.
Organic
Contaminant

Carbon
Tetrachloride
2-Butanone
(Methyl Ethyl
Ketone)
Benzene

Cyclohexane

1,2-Dichloro-
ethane
Trichloro-
ethylene

Toluene

Boiling Density
Point gm/cm3
°C

76.8 1.5833
25°C
79.6 0.7994
25°C

80.1 0.88

80.7 0.7731
25°C

84 1.257
87.3 1.4578
25°C

110.6 0.8647
25°C

Viscosity Water
cP Solubility
25°C mg/1

0.908 800
20°Ce
0.405 26,800

0.604 1770
25°C

0.894 58
25°C

0.779 8700
20°C
0.545 1100
25°CC

0.56 515-540
25°C

Vapor
Pressure
mm Hg
T,,°C

58.3
10°C
52.6
10°C

47.8
10°C

50.5
10°C

40.0
10°C
37.6
10°C

14.3
!0°C

Vapor
Pressure
mmHg
T2,°C

332.8
50°C
314.3
50°C

307.8
50°C

272.3
50°C

278.6
50°C
256.7
50°C

579.1
100°C

Henry's Law Octanol-
Constant Water
dimensionless Partition
25°C Coefficient

0.807 ±0.1 61" 676.1b'"
436.5CJ
0.001 01 1.820e
0.00112c-k

0.22 ±0.01" 134.90bAhJJ

7.27 ±0.81" 2754"

0.044 ± 0.004" 30.2"'1
0.397f 195"
0.38' 200"
0.372" 339r
0.27 ±0.014" 537"
490
-------
Table 1 -- Continued.
en
Organic
Contaminant
4-Methyl
2-Pentanone
Tetrachloro-
ethylene
n-Octane

Chloro-
benzene

Ethylbenzene

Xylenes

n-Decane

Dichloro-
Benzene
(3 isomers)
Dodecane
Boiling Density
Point gm/cm3
°C
116.6 0.802
121.3 1.613
25°C
126 0.6986
25°C

131.7 1.1007
25°C

136.2 0.8654
25°C

138.4 - 0.8577
144.4
0.8764
25°C

174.2 0.730

173- 1.2988
180 25°C
(ortho
isomer)
216.5 0.75
Viscosity
cP
25°C
0.545
0.844

0.508

0.753

0.631

0.608 -
0.802

0.838

1.044-
1.324

1.383
Water
Solubility
mg/1
19000
150
25°C
0.7
20°Ce

490
25°C

160
25°C

160-
180
25°C

0.052

80- 150
25°C

0.0034
Vapor
Pressure
mmHg
T,,°C
4.3
10°C
9.0
10°C
6.5
10°C

6.9
10°C

6.0
10°C

4.5 - 5.6
10°C

3.0
25°C
2.2
25°C

Vapor
Pressure
mmHg
T3,°C
381.0
100°C
400
100°C
368.7
100°C

323.7
100°C

295.7
100°C

238.9 -
280.8
100°C

77.7
100°C
67.1
100°C

19.5
100°C
Henry's Law
Constant
dimensionless
25°C
0.0063'
0.928 ±0.161"

121 ±20°

0.14 ±0.02°

0.323 ± 0.028°

0.20f
9400)
0.202 - 0.286C
0.214'

282.5 ±121°

0.048 - 0.073"

302.7 ± 100.9"
Octanol- Diffusion
Water Coefficient
Partition in Water
Coefficient cnrYday

400ic
407"
104,700'
151,356h'r

691.8"*'
955'

1412.5WM o.700w
1349' 20°C
0.3 80h 2°C
1412-
1585"
588.8 -
1584.9e'u
1349-
1585'

2399-
398 lb
2399-
2455e
1537'
13xl06h
Diffusion
Coefficient
in Air
cnvVday

4910f
5166.7h
20°C
4363s 0°C
6394°
26°C
7776°
59°C
6480s
30°C
6333"
20°C

5980f
5771.5h
20°C

Heat of
Vaporiz-
ation1"
kJ/mol
25°C
40.61
39.68

41.49

40.97

42.24

42.40 -
43.43

51.38

36.18-
49.00

61.51
Continued on next page.
-------
Table 1 - Continued.
o>
Organic
Contaminant

Naphthalene

1 -Methyl
naphthalene
Hexadecane
Phenanthrene

Gasoline

Boiling Density
Point gm/cm3
°C

218 0.97

244.8 1.020
286.9 0.773
340 0.98

0.73
0.7182"
20°C
Viscosity Water Vapor
cP Solubility Pressure
25 °C mg/1 mm Hg
Tp °C

32
25°C

28.5
3.032 0.0063 < 1
1.18

0.45 100 - 300
0.4 - 0.6" 30 - 120h
20°C
Vapor
Pressure
mm Hg
T2,°C

22.7
100°C

0.043
kg/m3
< 1

Henry's Law
Constant
dimensionless
25°C

0.02bj
0.051"
0.01 7 ±0.002"
0.01 82 ±
0.0016"

0.00161-"1
0.001 6 ±
0.00032"

Octanol- Diffusion
Water Coefficient
Partition in Water
Coefficient cnvVday

2239"-'
2344.2'
1738'
7413'

28,840e-'
37154'

Diffusion Heat of
Coefficient Vaporiz-
in Air ationb
cmVday kJ/mol
25°C
4432s 0°C

81.38
72.50

6272.6"
20°C

Superscripts
a-Baehr, 1987
g-Thomaetal., 1992
m-Juryetal., 1984
r - Miller et al., 1985
b - Lide, 1993
h - Lyman et al., 1991
n - Mackay and Shiu, 1981
s - Perry and Chilton, 1973
c - Newell et al., 1995
i-Ryanetal., 1988
o-Treybal, 1980
d-Huntetal., 1988
j - Jury et al., 1990
p - Tyn and Calus, 1975
e - Verschueren, 1983
k-Sanders, 1995
q-Valsaraj, 1988
f-Ongetal., 1992
1 - Johnson et al., 1990
-------
values that were thought to be reliable. For chemicals for which
their recommended values are available, they are listed in
Table 1. For the other chemicals, all reported values that were
located in the literature are listed to show the range in reported
values. The Henry's law constants listed in the table show that
at ambient temperatures, the alkanes and similar compounds,
such as 1-hexene and cyclohexane, have a strong preference
for the air phase rather than the aqueous phase, while the
chlorinated solvents and compounds that contain a benzene
ring tend to concentrate more in the aqueous phase. As the
number of benzene rings in the compound increases, its prefer-
ence for the aqueous phase increases. The ketones listed in
Table 1 also have a very strong preference for the water phase.

The partition coefficient is defined as the ratio of the equilibrium
concentration C of a dissolved substance in a system containing
two largely immiscible solvents. Thus, the octanol-water parti-
tion coefficient is defined as Kow = Coclano/Cwater. The octanol-
water partition coefficient has proven useful as a means to
predict soil absorption as well as biological uptake and
biomagnification and related phenomenon (Verschueren, 1983).
In general, the more hydrophobic a compound is, the greater its
octanol-water partition coefficient and the greater its absorption
onto soil organic matter (Karickhoff et al., 1979). However, this
generalization is limited to hydrophobic organic compounds and
soils which contain significant amounts of organic matter, on the
order of at least 0.1 percent (Schwarzenbach and Westall, 1981;
Weber et al., 1991). Most of the organic compounds listed in
Table 1 are at least moderately hydrophobic, thus the octanol/
water partition coefficient might be expected to indicate the
degree of absorption of these compounds in surface soils or
other soils with high organic carbon contents. It can be seen in
Table 1 that there are also some large differences in the reported
values for the octanol/water partition coefficients for a given
organic compound depending on the source of the data. Despite
these differences, the reported values show that most of the
compounds listed have a strong preference for organic matter
rather than the water phase, with the exception being the
ketones and methanol. The absorption of contaminants into the
soil organic matter will tend to limit the rate at which they can be
recovered in either the aqueous or gaseous phase.

To illustrate what the Henry's law constants and octanol-water
partition coefficients indicate about the distribution of an organic
chemical in the subsurface, a few calculations were carried out
using the equations given by Feenstra et al. (1991). The results
of these calculations are shown in Table 2. A surface soil of loam
texture with a bulk density of 1.28 gm/cm3, a porosity of 0.30, a
water saturation of 50 percent, and an organic matter content of
2 percent was assumed. Karickhoff et al.'s (1979) relationship
between the octanol-water partition coefficient and the adsorp-
tion coefficient, Kd, was assumed to be valid: Kd O.Bf^K^, where
f^, is the fraction of organic matter in the soil. In order to
demonstrate the effect of soil properties on the distribution of an
organic chemical, calculations were also done for the same
chemicals for a sandy soil of bulk density 1.86 gm/cm3, porosity
0.30, and organic matter 0.1 percent. Again, a 50 percent water
saturation was assumed.
Table 2 shows that in soils with high organic carbon content,
organic compounds may be highly associated with the solid
material. Calculations for 1,1,1-trichloroethane (TCA) were
carried out using the range of values that have been reported for
Kovv for this chemical to illustrate the difference this can make in
the calculated distributions. For soils with high organic matter
content there is very little difference as most of the chemical is
still associated with the solids. For low organic matter conditions
the difference in the distribution is significant, and the lower Kow
value means that more of the chemical is recoverable in the
water or air phase. Trichloroethylene (TCE) and TCA have
similar Kow values at ambient temperatures, but TCA has a
Henry's law constant that is greater than that of TCE at tempera-
tures around 20°C and, thus, much more of the TCA will be in the
air phase. TCE is a volatile organic compound but, at 20°C,
significantly more of its mass will be in the aqueous phase rather
than in the gas phase; a very significant proportion of it will be
associated with the solids. Acetone is highly volatile with a
boiling point of 56°C, but its extremely low Kow and Hc concentrate
it in the aqueous phase. Because acetone is miscible with water
and is a good solvent for many organic chemicals, acetone may
significantly increase the transport of less soluble organic chemi-
cals in ground water (Huling, 1989; Udell and Stewart, 1989).

The diffusion coefficient measures the rate at which molecules
spread down a concentration gradient, and is dependent on the
chemical nature of the system and the concentration, as well as
the temperature and pressure. As can be seen from the
coefficients listed in Table 1, diffusion in gases is much greater
than diffusion in liquids, which is due to the considerably higher
molecular concentration of liquids. When experimental data is
not available, the diffusion coefficient for gases can be estimated
fairly accurately by equations that have been developed based
on the kinetic theory of gases. For liquids, diffusion coefficients
cannot be estimated with the same degree of accuracy because
a sound theory of the structure of liquids has not been devel-
oped. However, empirical correlations have been developed
and can be used in the absence of laboratory data (Treybal,
1980). Observation of the values in the table shows that most of
the organic compounds for which values could be located fall in
the range of 5000 to 8000 cm2/day for diffusion in air; methanol
and acetone are again the exceptions with larger coefficients. All
of the water diffusion coefficients, also, fall in a rather narrow
range from 0.7 to 1.6 cm2/day.

The properties listed in Table 1 are for pure chemicals, and do
not consider the effects of a porous solid on the properties and
behavior of the chemical. The vapor pressure, the diffusion
coefficient in both air and water, and perhaps the viscosity, are
all significantly affected by the presence of the chemical in
porous media and the properties of that media. The partial
pressure of a liquid is dependent on the curvature of the interface
between the liquid and gaseous phases, and the values con-
tained in Table 1 are for a flat interface. When the interface is
curved, the partial pressure of the liquid is reduced. Although
this effect is very small in sandy soils with a less than one percent
reduction in vapor pressure, it becomes important in clay soils
when the pore sizes are less than approximately 106 cm,
-------
Table 2. Distribution of chemicals in low and high organic matter content soils.

1,1,1 -Trichloroethane
POO, = 300
1,1,1 -Trichloroethane
P = 147.9
oct
Trichloroethylene
20°C
Trichloroethylene
90°C
Acetone
Air
5%
6%
1.6%
30%
0.07%
High Organic
Water
5%
6%
4.6%
7%
85%
Matter
Solids
90%
88%
93.8%
63%
15%
Low
Air
26%
35%
14%
73%
0.08%
Organic
Water
23%
31%
35%
16%
99%
Matter
Solids
51%
34%
52%
11%
1%
causing a decrease in vapor pressure of approximately 40 per-
cent (Wilson etal., 1988). This effect can also be important when
the medium is dry and the remaining liquid has receded into the
smallest pores (Bear and Gilman, 1995). These capillarity
effects will determine the level of cleanup that can be achieved
by a venting process at a given temperature (Lingineni and Dhir,
1992).

Adsorption of the organic onto the solid phase or partitioning into
the soil organic matter can also have the effect of lowering the
partial pressure of an organic compound. Adsorption can occur
from the liquid onto the solid and, when the water content is very
low, from the vapor phase onto the soil surface (Lighty et al,
1990; Tognotti et al., 1991). Fares et al. (1995) have studied
desorption of TCE from soils, and their data shows that the
equilibrium vapor pressure of TCE as it desorbs from a soil is
approximately an order of magnitude lower than the partial vapor
pressure of TCE when no soil is present. Experiments per-
formed by Arthurs et al. (1995) showed that the rate of volatiliza-
tion of the liquid in the presence of a soil is about two orders of
magnitude slower than from the pure liquid, and that the vapor-
ization rate increases as the vapor pressure of the compound
increases. Fares et al. (1995) and Keyes and Silcox (1994)
found that the rate of desorption was linearly correlated with the
inverse of the soil particle diameter. Hatzinger and Alexander
(1995) found that organic compounds may become more tightly
bound to the soil or organic matter with time, which reduces their
desorption. Thus, the equilibrium partial pressure of a volatile
contaminant in the pore space and mass transfer from the
aqueous liquid or adsorbed phase will depend on the properties
of the chemical and the soil environment in which it resides.
The diffusion coefficients listed in the table are for bulk air or
water. In the pore spaces of a soil, diffusion in both the air and
water phase is reduced because of the reduced cross-sectional
area and increased path length caused by the presence of solid
and liquid obstacles (Millington, 1959). Diffusion coefficients in
porous media are a function of both the porosity of the soil and
the water (or air) content of the pores. At low water contents,
diffusivity in the water is also limited by the continuity of the water
phase. For diffusion in water in porous media, Porter etal. (1960)
found a nearly linear increase in effective diffusion as the water
content increased, ranging from 4 to 30 percent of its diffusion in
bulk water. Jin and Jury (1996) recommended the use of a
second model developed by Millington (1959) for predicting gas
phase diffusion in disturbed porous media: Ds/Da = a^n273, where
Ds is the diffusion coefficient of a gas through soil, Da is the
diffusion coefficient in free air, a is the volumetric air content of
the pores, and n is the porosity. They did not find a unique
relationship for gaseous diffusion in undisturbed soils due to
their heterogeneous nature. Measured gas phase diffusion in
undisturbed soils is both higher and lower than predicted by this
theory, but is not generally greater lhan about 40 percent of the
diffusion in air, and the diffusion drops off rapidly as the air-filled
porosity decreases.

Adsorption of water onto solid surfaces, particularly onto the
reactive surfaces of clays, will increase the viscosity of the water
in the layers immediately adjacent to the clay surface. Theoreti-
cal and experimental results of Kemper (1961 a, 1961b) indi-
cated that the first layer of water on the surface of a clay may
have a viscosity on the order of 10 times that of the bulk water,
and the viscosity of each adjacent layer of water then decreases
-------
rapidly to the viscosity of the bulk water. How much effect this
has on bulk flow in soils depends on the thickness of the water
films in proportion to the pore sizes. Neutral organic species will
generally not be adsorbed to the surface of the soil as strongly
as water. Therefore, neutral organics may have a smaller
effective viscosity relative to that of water in porous media,
allowing them to flow more readily. For clays that are highly
reactive and swell in the presence of water, research has shown
that the presence of organic chemicals may shrink the clay.
Cracks may form which allow a much greater flow of the organic
chemical than was possible with water (Anderson et al., 1985;
Brown and Thomas, 1987; Fernandez and Quigley, 1988).

Table 3 lists a few of the viscous oils that have been found
contaminating the subsurface. These oils are essentially non-
volatile and are not soluble to an appreciable degree in water.
Thus, they remain a separate liquid phase in the subsurface. All
of these oils are mixtures of many different hydrocarbons. Coal
tar and creosote also contain polycyclic aromatic hydrocarbons.
When oils such as these are spilled to the subsurface and are
exposed to air and water, "weathering" will occur, as the more
volatile hydrocarbons volatilize to the pore air, and the more
soluble hydrocarbons dissolve in the pore water. Water and air
moving past these oils while they are trapped in the subsurface
will enhance the weathering process. The loss of the "light"
hydrocarbons by the weathering process will increase the spe-
cific gravity and viscosity of the remaining oil, and lower the
surface and interfacial tensions. Measurements made in the
author's laboratory, Robert S. Kerr Environmental Research
Center, showed that a significant proportion of the crude oil was
volatilized at room temperature, causing a 7-fold increase in
viscosity. Creosote was found to contain few volatiles at room
temperature, and weathering did not change its viscosity signifi-
cantly. The specific gravity of both oils increased, and the
surface and interfacial tensions decreased by approximately 5 to
10 dynes/cm by the weathering. Mungan (1964, 1966) has
found that decreasing the interfacial tension in an immiscible
displacement will increase recovery of the oil. Although de-
creases in interfacial tension will favor recovery of these oils, that
may be offset by a decrease in mobility caused by the higher
viscosities.

Research in the author's laboratory has shown that oils such as
the crude oil listed in Table 3 flows more readily through some
silica sands than would be predicted based on the intrinsic
permeability of the sand measured with water and the density
and viscosity of the crude oil. This is likely due to the nonpolar
nature of these hydrocarbons which limits their adsorption to soil
surfaces. The greater mobility of the crude oil would give it a
greater tendency to spread as it enters the subsurface, but also
should aid in its recovery by a displacement process such as hot
water injection.

Mechanisms for Enhanced Recovery

In general, when an organic chemical is heated, its density is
reduced, its vapor pressure is increased, its adsorption onto
solid phases or absorption into soil organic matter is decreased,
and its molecular diffusion in the aqueous and gaseous phase is
increased (Isherwood et al., 1992). The viscosity of a liquid will
decrease as the temperature is increased, but the viscosity of
gases increases with temperature. Which of these effects of
heat is important for the enhanced recovery of a particular
contaminant depends mostly on the properties of the contami-
nant and the mechanism limiting the removal rate of the contami-
nant in the particular circumstance.

Available data on the expansion of organic chemicals such as
those listed in Table 1 with temperature shows that these
chemicals expand approximately 0.1 percent per degree Cel-
sius. Thus, increasing the temperature by 100°C will increase
the liquid volume by approximately 10 percent. Since the volume
of a gas is directly proportional to temperature given in Kelvin, a
100°C increase in temperature will cause approximately a 30 per-
cent increase in the gas volume. These changes are small
compared to the volume change that occurs when a liquid is
converted to a gas; water at 100°C has approximately a 1600-fold
increase in volume when it is converted from a liquid to a vapor.

The expansion of liquids with temperature causes a reduction in
the interaction between molecules, and thus a reduction in its
viscosity. For the organic chemicals listed in Table 1, generally
there is about a one percent change in viscosity per degree
Celsius. Thus, the higher the viscosity of the liquid at ambient
temperatures, the greater the reduction in viscosity as the
temperature is increased. The viscosity of gases at ambient
temperatures is approximately one to two orders of magnitude
lower than the viscosity of liquids. However, the increase in the
velocity of gas molecules with temperature is such that it causes
greater interaction between molecules as the temperature in-
creases, causing an increase in viscosity with temperature. This
increase is proportional to the temperature in degrees Kelvin, so
that a 100°C increase in temperature will increase the viscosity
of a gas by about 30 percent.

The effect of temperature on solubility is dependent on the
chemical. Increasing temperature will reduce the water-water,
water-solute, and solute-solute interactions, so the net effect of
temperature on solubility will depend on which interactions are
affected to the greatest extent (Yalkowsky and Banerjee, 1992).
Thus, some chemicals show increasing solubility with tempera-
ture while others show decreasing solubility with temperature.
Maximum or minimum solubilities with temperature have also
been found for some chemicals; many organic liquids exhibit
minima in solubility at about room temperature (Yalkowsky and
Banerjee, 1992). Measurements by Stephenson (1992) and the
data compiled by Horvath (1982) show that the solubility of the
organic chemicals listed in Table 1 often decreases in the
temperature range of 0°C to 90°C, but the change in solubility in
this temperature range is generally less than a factor of two.

Vapor pressures always increase with temperature. For the
organics listed that have a boiling point of less than 100°C, the
vapor pressure increases by a factor of 5 to 7 as the temperature
increases from 10°C to 50°C. For those compounds that have
a boiling point greater than 100°C, their vapor pressure generally
increases by a factor of 40 to 50 by raising the temperature from
10°C to 100°C. Limited data on the desorption of organics from
-------
Table 3. Properties of some oily contaminants.

Automatic
Transmission
Fluid"
Coal Tarb

Coal Tar*

Creosote11

Crude Oil"

Boiling
Range
> 350°C

50% can be
distilled at
270°C

45 to 65%
can be
distilled at
315°Ce

Specific
Gravity
0.875
20°C

25°C 0.9744
60°C 0.9469
85°C 0.9263
7°C 1.028
15°C 1.017
38°C 0.991
60°C 0.985
10°C 1.1060
20°C 1.1027
30°C 1.0957
40°C 1.0893
50°C 1.0816
10°C 0.8953
20°C 0.8883
30°C 0.8820
40°C 0.8760
50°C 0.8680
Viscosity Water Vapor
cp Solubility Pressure
mg/1 mm Hg
<50 <2xlOJl
20°C

25°C 41.4
60°C 1.65
85°C 1.16
7°C 18.98
50°C 5.04
60°C 3.89

10°C 35.7
20°C 19.8
30°C 12.4
40°C 8.57
50°C 6.17
10°C 160.2
20°C 63.0
30°C 34.8
40°C 23.2
50°C 16.4
Surface
Tension
dynes/cm
33.7

28.8

10°C 32.4
20°C 33.5
30°C 29.0
40°C 25.0
50°C 26.8
10°C 26.2
2.0°C 24.5
30°C 23.2
40°C 23.3
50°C 22.8
Interfacial
Tension
dynes/cm

22
22°C

9.65 10°C
7.83 20°C
6.16 30°C
5.31 40°C
5.90 50°C
22.0 10°C
21.020°C
20.5 30°C
20.2 40°C
21.4 50°C
a - Abdul et al., 1990 b - Johnson and Guffey, 1990
e - American Wood Preservers' Association Standards
c - Villaume et al., 1983 d - unpublished data from the author's lab
soils shows that the exponential increase in the vapor pressure
with temperature also holds when the organic chemical is in the
presence of soils (Fares et al., 1995).

The combination of only small changes in solubility with tem-
perature but large increases in vapor pressure results in in-
creases in Henry's constant as a function of temperature.
However, very few measurements of Henry's constants for
chemicals of environmental concern as a function of tempera-
ture have been made, and most of these measurements are over
a limited temperature range. Heron et al. (1996) calculated and
measured Hc values for TCE as a function of temperature and
found an order of magnitude increase when the temperature was
raised from 20°C to 90°C. For the more soluble compounds such
as dichloromethane or 2-butanone, and the water-miscible com-
pounds such as acetone and methanol, Hc may not be influenced
significantly by temperature.

Few measurements of Kow and/or Kd have been made as a
function of temperature, and most of the measurements that
have been made are over very small temperature ranges.
Although it has been shown for some systems that adsorption
may increase with temperature over narrow temperature ranges
(Weber et al., 1983), adsorption is, in general, an exothermic
process and, thus, will decrease as the temperature increases.
The magnitude of the effect of temperature is dependent on the
particular chemical, the soil, and the water content, as these
factors will determine the mechanism causing the adsorption
(Cancela et al., 1992; Piatt et al., 1996). Heron et al. (1996)
showed theoretically, based on heats of sorption, that adsorp-
tion from the aqueous phase onto soils can be expected to
decrease by a factor of approximately 2.2 as the temperature is
increased from 20°C to 90°C. Adsorption from the vapor phase
onto dry soils generally has a larger heat of sorption, which leads
to a greater influence of temperature on the adsorption process.
For TCE, Heron et al. (1996) found approximately an order of
magnitude decrease in adsorption onto dry soil as the tempera-
ture was increased from 20°C to 90°C. For high molecular
weight organics such as PCBs, a large fraction of the organic
may remain adsorbed to the soil at ambient temperatures, and
significantly higher temperatures (300°C to 400°C) may be
required for desorption to occur (Uzgiris et al., 1995).

Measured data has shown that the diffusion coefficient in liquids
is proportional to temperature in degrees Kelvin. Increasing the
temperature from 10°C to 100°C will increase the diffusion of a
10
-------
solute in the aqueous phase by approximately 30 percent
(Treybal, 1980). The diffusion coefficient for gases is also
dependent on temperature. Observation of the theoretical
equation for diffusivity in the gas phase developed for mixtures
of nonpolar gases or of a polar with a nonpolar gas shows that
the diffusivity varies almost as T3/2 (Treybal, 1980). Increasing
the temperature from 10°C to 100°C will increase diffusion in the
air phase by approximately 50 percent, while a temperature
increase from 10°C to 300°C will increase diffusion by approxi-
mately 200 percent.

Essentially all of these changes with temperature can aid in the
recovery of contaminants from the subsurface. The thermal
expansion of a liquid with its accompanying decrease in viscos-
ity will allow the heated liquid to flow more readily. For gases, the
expansion with temperature will be largely offset by the increase
in viscosity. However, since the viscosity of gases is approxi-
mately two orders of magnitude lower than the viscosity of
liquids, conversion of a liquid to a gas will greatly increase its
mobility. The act of expansion itself will aid in moving the fluids
out of the pore space, with the greatest effects coming from the
vaporization of a liquid to a gas. The increased diffusion of
contaminants as the temperature increases in both the aqueous
and gaseous phases will help to move contaminants from areas
of low permeability to areas of high permeability and speed their
recovery.

To demonstrate the effects of temperature on the distribution of
organic contaminants between the phases in the subsurface,
calculations were carried out using the data of Heron et al. (1996)
for TCE at 90°C. The results are shown in Table 2. It can be seen
that raising the temperature to 90°C significantly increases the
concentration in the air phase under both the high and low soil
organic matter conditions, while significantly decreasing the
amount that is associated with the solids. Only small amounts
remain in the liquid phase. Thus, as the temperature is in-
creased, significantly more of the TCE can be recovered in the
vapor phase. If the high organic mattercontent soil is considered
under water saturated conditions, the amount of TCE in the
water would approximately double as the temperature was
increased from 20°C to 90°C, but 82 percent of the TCE would
remain adsorbed to thesolids. Underthe low organic matter/water
saturated conditions, there would be approximately a 30 percent
increase in the amount of TCE in the water phase when the
temperature is increased from 20°C to 90°C, leaving approxi-
mately 25 percent adsorbed to the solids.

This small effect of temperature on the concentration in the
aqueous phase shows that raising the temperature would have
a limited effect on the recovery in a pump-and-treat system. For
the volatile and semivolatile organic compounds, such as those
listed in Table 1, the enhanced vapor pressure and rate of
vaporization are generally the most important mechanisms for
enhanced recovery using the in-situ heat based remediation
techniques. Some of the most volatile compounds, which
includes TCE, benzene, and toluene, can be removed fairly
efficiently from sandy soils by vacuum extraction alone (Ho and
Udell, 1992; Gauglitz et al., 1994; Shah et al., 1995), and
laboratory experiments on vacuum extraction have shown that
the addition of heat had little effect on the vaporization of the less
volatile compounds. For the higher boiling point compounds and
when clays are present in the subsurface, the addition of heat as
part of the remediation process will significantly increase volatil-
ization and enhance the vacuum extraction process (Lingineni
and Dhir, 1992). Recovery of most of these chemicals from the
subsurface will be enhanced by either steam or hot air injection
or by electrical heating processes.

For the volatile and semivolatile contaminants, steam stripping
and steam distillation can also be important recovery mecha-
nisms (Dev et al., 1989; Stewart and Udell, 1988). Steam
distillation occurs when an immiscible liquid is present along with
water, as the mixture of immiscible liquids will boil when the total
pressure reaches one atmosphere, rather than when the pres-
sure of the individual component reaches one atmosphere.
Because both liquids are contributing to the vapor pressure, the
vapor pressure reaches one atmosphere at a lower temperature
than either of the individual components would (Atkins, 1986).
Steam stripping enhances volatilization of a volatile organic
compound by removing the vapor phase from contact with the
aqueous phase, thus preventing the liquid and vapor phases
from reaching equilibrium and allowing volatilization to continue.
Steam stripping becomes important when an immiscible phase
is not present (Dev et al., 1989).

For the types of contaminants listed in Table 3, the greatest
enhancement effect coming from the addition of heat is likely to
be a reduction in the viscosity of the oil phase. Highly viscous oils
will generally show a substantial decrease in viscosity with only
a moderate temperature increase above ambient temperatures
(Herbeck et al., 1976), and the rate of decrease with temperature
then drops off rapidly with continuing increases in temperature.
Edmondson (1965) found that the greater the dependence of
viscosity of the oil on temperature, the greater the increase in its
recovery by a hot water displacement as the temperature in-
creased. Other mechanisms for the increased recovery of oils
by hot water include the thermal swelling of liquids (Willman et
al., 1961), shifts in the relative permeabilities to oil and water with
temperature, and decreases in the residual oil saturation
(Edmondson, 1965; Davidson, 1969; Poston et al., 1970; Davis
and Lien, 1993). Decreases in the interfacial tension with
temperature for contaminants such as creosote may also aid in
its recovery from the subsurface. Different researchers have
found shifts of varying magnitudes and directions in relative
permeability curves, but in all cases the increase in oil recovery
as the temperature increases always appears to be greater than
would be predicted based on the viscosity reduction alone.
Capillary pressure-saturation curves measured for two phase
water/oil systems have shown substantial decreases in the
residual oil phase as the temperature increased (Davis, 1994),
and thus, a greater portion of the oil may be recoverable as the
temperature is increased.

Heat-based In-situ Remediation Techniques

There are three general methods that can be used to inject or
apply heat to the subsurface to enhance remediation: injection
in the form of hot gases such as steam or air, electromagnetic
11
-------
energy heating, and hot water injection. Another thermal
remediation technique that relies on thermal conduction of soil to
heat the subsurface is also under development (Iben et al.,
1996), but will not be discussed here. All of these methods were
first developed by the petroleum industry for enhanced oil
recovery, and have more recently been adapted to soil and
aquifer remediation applications. The two applications have
significantly different objectives. In oil recovery operations, the
reservoir initially has a large oil saturation, and the objective is
to recover as much as possible economically. In these opera-
tions, a large residual oil saturation of as much as 50 percent or
more may be acceptable. In contamination remediation applica-
tions, the initial saturation of the contaminant may be anywhere
from essentially fully saturated to less than residual saturation,
and the objective is to reduce the contaminant concentration to
very low levels. The techniques of steam injection, electrical
energy application, and hot water injection have been the
subject of extensive research and development, and it has been
established thatthese techniques are effective for the remediation
of organic contaminants when they are appropriately applied
(Fulton et al., 1991; Davis and Lien, 1993; U.S. EPA, 1995a;
Newmark and Aines, 1995).

Injection of hot air has been tried in the laboratory and found to
enhance the removal of contaminants from one-dimensional soil
columns (Lingineni and Dhir, 1992; Shah etal., 1995). However,
the use of hot air in the field is limited by the very low heat
capacity of air (approximately 1 kJ/kg °C) (Ramey, 1967).
Steam, with a heat capacity that is approximately four times that
of air (approximately 4 kJ/kg °C), and heat of evaporation of more
than 2000 kJ/kg, has been used successfully to heat soils,
aquifers and reservoirs to enhance the recovery of contaminants
and oils. However, the injection of steam will always leave
behind a residual water saturation (Stewart and Udell, 1988),
and contaminants that have a significant solubility in water may
remain at high concentrations in this residual water or may even
appear to increase in concentration (Udell and Stewart, 1989;
U.S. EPA, 1991). For these situations, recovery of the contami-
nants may require that the soil be dried, and hot air injection may
be applicable (Farrington, 1996).

Steam, hot air and hot water injection rely on contact between the
injected fluid and the contaminant for the transfer of heat to and
recovery of the contaminant. Steam injection will displace
mobile contaminants in front of the steam as well as vaporize
volatile residual contaminants, and therefore can recover vola-
tile contaminants in both the liquid or vapor phase. Hot air
injection has been used to recover contaminants only in the
vapor phase. Hot water injection generally recovers contami-
nants only in the liquid phase. Thus, steam injection is appli-
cable to volatile and semivolatile organic compounds that are
immiscible with water, hot air is applicable to volatile and
semivolatile organics that are water soluble, and hot water
injection is applicable for the oils that have low volatility and very
low solubility in water. The main mechanism for enhanced
recovery using hot water is generally a reduction in the viscosity.
Changes in relative permeability and reductions in residual
saturation are likely to also aid in the recovery of nonvolatile oils.
Hot water injection is most likely effective only when the non-
aqueous phase is present in quantities greater than the residual
saturation, as the main recovery mechanism is the physical
displacement of the nonaqueous phase. Hot water injection may
be most effective for light oils that are floating on top of the water
table, as the lower-density hot. water has a tendency to rise if
injected below the water table. For oils that are more dense than
water at ambient temperatures but less dense than water at the
displacement temperature, heating of the subsurface by hot
water injection may help to float these oils, which may aid in their
recovery (Johnson and Guffey, 1990). Steam injection has a
definite advantage over hot water injection when the contami-
nants have a low boiling point and are present as an immiscible
phase, and thus can be steam distilled at the temperatures
achieved by steam injection (Willman et al., 1961). Field trials
have shown that steam injection can be carried out above or
below the water table (Udell and Stewart, 1989; U.S. EPA, 1991;
Aines etal., 1992).

There are limitations on the pressures that can be used for steam
and hot water displacement processes, and this limits the
viscosity of the fluid that can be displaced from a media with a
certain permeability. However, volatilization processes using
steam or hot air may still be possible in low permeability media
(Farrington, 1996), and for highly viscous oil, it may be possible
to heat the oil and lower its viscosity sufficiently to recover at
least a portion of the oil by either a displacement process or
gravity drainage (Hall and Bowman, 1973; Vogel, 1992).

Electrical energy has been applied to the soil in the low fre-
quency range used for electrical power (called electromagnetic
(EM), alternating current (AC), or resistivity heating) as well as
in the radio frequency (RF) range. When EM heating is used, the
water in the pore spaces of the soil absorbs essentially all the
applied energy, so the evaporation of water limits the transport
of energy in the soil and, therefore, limits the heating process.
Thus, for the low frequency methods, the boiling point of water
is the highest temperature that can be achieved. For semivolatile
organic contaminants, the vapor pressure at 100°C may not be
adequate to effectively recover the contaminants. For this
reason, researchers have also developed the use of RF energy
for soil heating. RF energy can be absorbed by the soil itself, and
thus is not limited by a lack of water in the pore space. Using RF
energy, the upper temperature limit of the technique is 300°C to
400°C (Dev, 1993; Sresty, 1994). For electrical heating, the
electrical properties of the soil and the presence of water are
important in determining the efficiency of the heating process
(Dev et al., 1989; Marley et al., 1993). The electrical heating
techniques are recommended for the removal of organic con-
taminants which exhibit a vapor pressure of at least 10 mm Hg
in the treatment temperature range (Sresty, 1994). There is
some evidence that high molecular weight organics, such as
organopesticides, can be broken down to simpler organics such
as acetone, benzene and toluene, at the temperatures and
conditions that can be achieved by RF heating (U.S. EPA,
1995b&c; Swanstrom and Besrner, 1995). Electrical heating
has been proven effective in sandy media (Dev, 1986), and also
has a greater potential than steam or hot water injection to be
effective in less permeable media such as clays. The higher
water content generally found in the clay will aid in directing the
12
-------
electromagnetic energy to the clay and allow a faster heating
rate and higher temperatures to be achieved. RF heating,
however, is limited to the unsaturated zone. For contaminants
trapped below the water table, dewatering would have to be
done prior to electrical heating (U.S. EPA, 1995b).

Because steam injection (at least in its initial stages) and hot
water injection are displacement processes, they can also
recover nonvolatile contaminants dissolved in the aqueous
phase, such as salts (Vaughan et al., 1993), but heat does not
necessarily enhance the recovery of this type of inorganic
contaminant. Metals, with the exception of mercury, cannot be
recovered from soils by thermal means. Mercury has a signifi-
cant vapor pressure at ambient temperatures, and it increases
as the temperature increases. Adsorption onto soils and other
materials can reduce its partial vapor pressure significantly, and
it was found that drying soil samples to 100°C did not recover
measurable amounts of mercury. At temperatures of 200°C and
greater, significant amounts of mercury can be recovered from
soils, reducing the residual remaining in the soil to as little as 1
part per million at 400°C (Dewing and Schluter, 1994).

Each of these thermal methods is generally applicable only to
certain types of contaminated sites, and it is important that the
appropriate heat-based remediation technique is chosen for a
given site. The choice of technique must be based on both the
characteristics of the subsurface and of the contaminants to be
recovered. Steam or hot air injection or the electrical heating
techniques are generally applicable for the types of chemicals
that are listed in Table 1, while hot water injection is generally
applicable for the nonvolatile oils listed in Table 3. The perme-
ability of the media, the amount and type of heterogeneity, the
amount of adsorption, and the solubility of the contaminant must
all be considered when choosing between the technologies.
Electrical heating may be favored in low permeable media and
when there is significant heterogeneity. For highly soluble
contaminants, drying the soil may be necessary and, thus, hot air
or RF heating may be more applicable. Because desorption can
be aslow process, highertemperaturesand/orlonger remediation
times may be necessary when adsorption is significant.

Figure 1 can be used as a quick guide to determine which of the
techniques would likely be applicable for a given situation; in
some cases, more than one technique may be applicable. The
principle that has been applied in developing this figure is to
recommend the least severe technique, in terms of temperature
and pressure requirements, that is likely to be able to recover the
contaminants. For example, although hot water and steam
injection may both be able to recover a nonvolatile, viscous oil,
hot water injection is recommended because it will generally
recover the same amount of this type of oil (Willman et al., 1961)
at a lower temperature. Equipment and facilities for generating
and handling hot water are relatively simple and inexpensive
(Harmsen, 1971), but the generation and transport of steam
involves more complex and expensive systems. Higher operat-
ing temperatures also mean greater safety risks (Herbeck et al.,
1976). The Issue Paper specific to that technique can then be
consulted for further information.
Comparison to Other In-situ Techniques

The one significant advantage of heat-based remediation tech-
niques over other in-situ remediation techniques is that these
methods do not require that chemicals of any sort be injected into
the subsurface as part of the remediation effort. This is a very
significant advantage over the surfactant and cosolvent tech-
niques because surfactants and cosolvents may themselves
have toxic properties, and it may not be possible to recover all of
the injected chemicals. Also, when surfactants or cosolvents are
used, the technique may be limited by a lack of contact between
the injected chemical and the contaminants, which can be
caused by low permeability layers within the media or by reduc-
tions in relative permeability to one phase because of the
presence in the pores of another phase (Peters et al., 1991).
With the in-situ heating techniques discussed in these Issue
Papers, heating of the entire area to be treated has generally
been accomplished (Aines et al., 1992; Gauglitz et al., 1994).

These heating techniques can be used with a technique such as
vacuum extraction, with benefits that may be significantly greater
than for either process used separately (Udell and Stewart,
1989; Jarosch et al., 1994). Also, these processes are appli-
cable in heavily contaminated soils, the "hot spots" of contami-
nated sites, which generally are very important to clean up in
order to stop the spread of the contamination, and where
biological treatment may not be effective (Johnson and Guffey,
1990; Aines etal., 1992).

These thermal techniques initially may be limited by subsurface
heterogeneities, which affects all other in-situ remediation tech-
niques. When low permeability clay lenses are present in an
aquifer, the injected fluids often bypass these low permeability
areas and, therefore, do not contact the contaminants contained
within them. With time, however, the heat will be conducted into
the lower permeability areas. Also, the Dynamic Underground
Stripping Process, developed by the Lawrence Livermore Na-
tional Laboratory, circumvented this problem for the case where
relatively thick clay layers are interbeded with sandy layers by
combining both steam injection and electromagnetic heating
with vacuum extraction (Newmark and Aines, 1995; Yow et al.,
1995).

Research has shown that complete desorption of chemicals
from clay soils, or soils containing a significant amount of natural
organic material, may require extreme temperature conditions
(Lighty et al., 1988; Tognotti et al., 1991), which may not be
achievable in-situ. Thus, in many cases, a secondary or polish-
ing step may be required to achieve very low contaminant
concentrations (Yow et al., 1995). Hot water injection or shallow
steam injection applications where low temperature and pres-
sures are used may leave the subsurface system amenable to
bioremediation. In fact, raising the temperature above ambient
temperatures may, in many instances, enhance naturally occur-
ring biodegradation of contaminants (Isherwood et al., 1992).
However, if steam is injected into the deeper subsurface at high
temperatures and pressures, or if the soil is heated to high
temperatures using RF heating, the soil will likely require cooling
13
-------
Volatile
Contaminant?
Yes
No
Steam or
Hot Air
Injection
or
No Sandy
•«— Media ?
Yes
Semivolatile
Contaminant ?

Yes
Sandy
Media ?
Yes
No
Air Sparging w
No
Unsaturated
Conditions ?
Yes
Unsaturated
Conditions ?
Fes
Nonvolatile
Contaminant ?
Yes
Sandy
Media ?
Yes
Steam or Hot
Air Injection
Figure 1. Flow Chart to indicate which of the thermal techniques may be applicable for a particular site.
before reestablishment of the microbial population can take
place (U.S. EPA, 1991).

Notice

The U.S. Environmental Protection Agency through its Office of
Research and Development funded the research described
here. It has been subjected to the Agency's peer and adminis-
trative review and has been approved for publication as an EPA
document. Mention of trade names or commercial products
does not constitute endorsement or recommendation for use.

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