SOIL

TECHNOLOGY
ELSEVIER

Soil Technology 10 (1997) 133-153

Soil interactions with petroleum hydrocarbons:

Abiotic processes
P. Fine, E.R. Graber * , B. Yaron
Institute

of Soils and Water, ARO, The Volcani

Received

18 January

Center,

P.O. Box 6, Bet Dagan

1995; accepted 22 January

50250, Israel

1996

Abstract
Soil and groundwater resources in many parts of the world are threatened by spilled petroleum
products, These products generally consist of complex mixtures of volatile hydrocarbons with
different vapor pressures. The volatilization of light hydrocarbon fractions leads to changes in
viscosity and density of the residual nonaqueous liquid. This may cause changes in the transport
characteristics of the porous matrix and of the residual liquid. Differing volatilization
and
solubility characteristics result in differential distribution of released hydrocarbon components in
air, soil, and water environmental compartments. Soil frequently serves as the site of petroleum
spills and hence the capacity of the soil to filter, retain, or release hydrocarbons is fundamental in
determining the type and extent of environmental contamination. Retention, volatilization, and
transport of hydrocarbons as affected by soil physical and chemical properties is reviewed.
Keywords:

Petroleum;

Soil; Retention;

Volatilization;

Transport

1. Introduction
Soil and groundwater contamination by leaking petroleum products threaten important resources,jeopardize local and regional ecological systems,and may even pose the
threat of explosion in urban areas.Soil frequently serves as the site of petroleum spills
and hence the capacity of the soil compartment to filter, retain, or releasehydrocarbons
will be fundamental in determining the type and extent of environmental contamination.

* Corresponding
vwgraber@volcani.agri.gov.il.

author.

Tel.:

+ 972-3-9683307;

00933-3630/97/$15.00
PI2 SO933-3630(96)00088-8

Copyright

0 1997 Elsevier

fax:

+ 972-3-9604017;

Science B.V. All rights reserved.

e-mail:

134

P. Fine et al. /Soil

Technology

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133-153

Extensive environmental contamination by hydrocarbons has underscored the importance of understanding the dynamics of hydrocarbon distribution in different environmental compartments. The fate of petroleum products released into the soil will be
particularly varied because these products generally consist of complex mixtures of
hydrocarbons with greatly differing vapor pressures and water solubilities. Differences
in these physical and chemical properties will lead to differential distribution of released
hydrocarbon components in air, soil, and water.
The redistribution and fate of petroleum hydrocarbons spilled on the land surface will
depend on both biotic and abiotic processes. The abiotic processes occurring within
porous media which are instrumental in controlling hydrocarbon distribution include
sorption, volatilization, transformation, and transport. Sorption of hydrocarbon molecules
at the solid surface may occur from the nonaqueous liquid, vapor, or aqueous phases.
Vaporization from the nonaqueous liquid, or desorption of sorbed molecules to the vapor
or aqueous phases may also play an important role in hydrocarbon redistribution in the
soil. Ultimately, hydrocarbons are transported either in bulk, as a nonaqueous liquid, in
vapor, or in low concentrations in the aqueous phase.
Abiotic aspects of soil-petroleum
hydrocarbon interactions were reviewed recently
by Calabrese and Kostecki (19881, Yaron (1989), Mercer and Cohen (19901, and
Kostecki and Calabrese (1991). The aim of the current work is not a general literature
review, rather, a discussion emphasizing the main impacts of soil materials on the fate of
petroleum products in the soil compartment. Soil properties including mineralogy,
texture, and moisture status, and their effect on sorption, retention, volatilization, and
transport will be presented and discussed based on results from our own research group
(Acher et al., 1989; Yaron, 1989; Yaron et al., 1989; Galin et al., 1990a; Galin et al.,
1990b; Fine and Yaron, 1993; Gerstl et al., 1994; Nye et al., 1994; Jarsjo et al., 1994.
After a petroleum spill on the land surface, petroleum hydrocarbon components will
be redistributed in the soil. Retention on the solid phase will occur by entrapment in
pores or sorption at mineral and organic matter surfaces. The highly volatile fraction will
volatilize into the gas phase of the porous medium. From there it may be lost to the
atmosphere, sorbed onto soil solids, or dissolved into soil water or groundwater. Less
volatile components will be transported in the nonaqueous phase through the porous
medium. Finite but differing aqueous solubilities for the disparate components will also
result in differential dissolution and transport as solutes in soil water. If the amount of
petroleum in the soil zone is greater than its retention capacity, the hydrocarbon mixture
will travel into the vadose zone as a separate, nonaqueous phase. Petroleum-soil
interactions will be discussed in the light of this scenario.

2. Materials

and methods

The experiments reviewed below were performed on a broad spectrum of soils whose
characteristics are summarized in Tables 1 and 2. Five petroleum hydrocarbons (mxylene, isopropylbenzene (ps-cumene), t-butyl benzene, n-decane and n-dodecane) and
a commercial petroleum product kerosene characterized by a mixture of more than 100
different hydrocarbons were used in the experiments.

P. Fine et al./Soil Technology 10 (1997) 133-153

Table 1
Characteristics
Soil series
and
horizon

of soils used in the experiments

Texture

(wt%)

clay

silt

SSA
sand

(after
(m/g)

135

Gerstl et al., 1994)

organic
matter
(wt%)

Moisture
HYG

very-fine
clayey, montmorillonitic,
thermic typic chromoxerert
74.4
10.6 - -15.0
ii6
9.6
2. Carmel (Ap): very-fine
clayey, montmorillonitic,
thermic typic pelloxerert
62.5
30.4
7.1
5.1
8.4
3. Nahsholim (Ap): fine-clayey,
montmorillonitic,
thermic typic chromoxerert
54.1
37.0
8.9
1.9
6.8
4. Nahal Oz (Ap): fine-loamy,
mixed, thermic calcic haploxeralf
18.1
30.2
51.7
2.0
2.0
5. Hermonit: fine clayey, mixed, mesic typic rhodoxeralf
(Ad;
29.6
53.6
16.8
2.0
4.3
(BQ)
56.4
34.4
9.2
0.65
6.2
6. Fazael (Bt): fine-loamy,
mixed, hyperthermic
typic haplargid
28.3
44.8
24.0
0.60
4.4
7. Netanya 8 (Bt2): fine-loamy,
mixed, thermic typic rhodoxeralf
25.3
7.3
67.4
0.34
4.1
8. Netanya 6 (Bt2): tine-loamy,
mixed, thermic palic rhodoxeralf
35.2
14.5
50.3
0.47
5.9
9. Mitzpe Masua (A): tine-loamy,
carbonatic, thermic lithic haploxeroll
19.6
59.0
21.4
5.20
2.8
10. Sharon 2 (Bw): sandy, siliceous, thermic typic xerochrep
5.1
2.2
92.7
0.11
0.48
11. Dune sand
0.3
1.2
98.5
0.01
0.35
12. Bet Dagan (Ap): loamy, mixed, thermic typic haploxeralf
12
68
0.5
0.8
13. Gilat (Ap): fine-loamy,
mixed, thermic calcic haploxeralf
16
52
44
117
0.8
2.9
14. Oxfordshire,
UK (Evesham clay) (A)
35
300
7.3
6.5

content

(wt%)

-33kPaC

-1OOkPa

49.0

42.0

45.4

38.2

30.2

25.8

18.3

17.8

34.3
34.1

18.5
25.8

32.3

20.8

17.6

12.8

25.4

21.2

33.1

23.2

3.4

2.8

3.1

2.6

12.0

19

35.0

1. Golan (Ap):

a Specific surface area.

b Hygroscopic
moisture content.
Pressure

2.1. Experimental procedures

Kerosene residual capacity (KRC) of moist soils was determined after pre-adjusting
soil moisture by meansof pressureplates. The moistenedsoil cylinder was immersedin
keroseneto a depth of 2 cm for 72 h. The soil cylinder was then turned upside-downand
re-equilibrated for another 72 h. The redistribution of kerosenewas performed at room
temperature (22 f 3C) in seateddesiccatorsover open vesselsof kerosene and water.
The kerosene content of the soils was determined in sub-samplestaken immediately
below the exposed surface. All keroseneresidual content determinations were made in
triplicate.

136

P. Fine et d/Soil

Table 2
Characteristics
of the soils used in transport
et al., 1994; Jarsjo et al., 1994)
Soil

Coarse sand 1
Coarse sand 2
Medium sand
Fine sand
Sandy loam 1
Sandy loam 2
Loamy mont
Clay mont
Glacial clay
Post gl clay
Peat

Texture

a (%)

clay

silt

0
-

19
15
16
40
51
44
-

14
18
36
17
21
25

a According to the USDA

b In KRC experiments.
Montmorillonitic.

Technology

experiments

Org. matter
sand

(%)

100
86
100
100
67
67
48
43
28
31
-

0.1
0.4
0.1
0.1
5.4
4.4
0.005
0.012
1.3
2.6
27.8

10 (1997)

(after
Bulk
density

133-153

Galin et al., 1990a; Galin et al., 1990b; Gerstl

Hygroscopic
water

Water ret.
capacity

(g cmm3) (%I

(wt%)

WRC)
(wt%)

1.82
1.80
1.84
1.73
1.42
1.38
1.47
1.39
1.37
1.44
0.68

0.35
0.28
0.40
0.48
2.46
2.29
2.5
4.9
3.19
3.36
5.03

1.0
10
2.4
2.8
47
46
19
28
44
50
74

Total
porosity

30
30
29
33
44
46
42
54
44
40
63

system of classification.

Volatilization experiments were performed in glass petri dishes (9.4 cm in diameter

and 1.1 cm in height) which were packed with 50 g of air-dry sand in a uniform 4 mm
layer. Kerosene was applied to each soil to the pre-determined kerosene retention
capacity. The experiments were carried out in a constant temperature room at 27C for
14 d. Kerosene loss was determined by gravimetric measurements daily, and gas
chromatographic identification of residual kerosene was made at 1, 2, 5, 7, and 14 d
after application. The experiments were performed in triplicate.
Volatilization of kerosene from contaminated soils was also examined in an outdoors
enhanced volatilization system with induced air flow (Fine and Yaron, 1993). A venting
chamber was designed to accommodate eight 10 L containers. An industrial centrifugal
fan in the ceiling of the chamber created a depression of = 350 Pa which forced air to
flow through the soil; air flows were calculated from measured air permeability and the
depression created by the fan.
Sorption-desorption isotherms of hydrocarbons from and into the vapor phase were
determined at constant temperature. Soil (5 g) was weighed into small vials (4.5 cm2
evaporative surface, 5 cm long) which were placed in glass jars (1 L). A vial containing
kerosene (5 mL), providing the vapor source, was placed in the center of each jar which
was then closed and sealed with Teflon tape. A rubber septum was fitted to the lids of
each jar to enable gas samples to be taken with a gastight syringe. Control jars (without
soil) were prepared for analysis of the vapor. The experiment was carried out with five
replicates at 27C for 7 weeks. Adsorption was carried out at 27C for 3 weeks. During
this time the atmospheric composition above the soil samples was checked periodically.
Desorption was achieved by leaving the soil samples open to the ambient atmosphere for
four weeks. Residual kerosene was analyzed in a time series. These experiments were
carried out in triplicate.

P. Fine et al./Soil

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137

Kerosene conductivity experiments were conducted in glass columns with a 51 mm

i.d. and a height of 100 mm, plugged at both ends with rubber stoppers covered with Al
foil and penetrated fully by glass tubes. The height of the soil column was 70 mm. The
columns were packed using a funnel connected to a rubber tube. By gradually raising the
funnel, the soil was uniformly packed into the cylinder from the bottom upward,
avoiding gravitational fractionation of particles. This procedure resulted in uniform
packing densities of 1.84 g/cm3 for the sand and 1.47 and 1.39 g/cm3 for the loam and
clay soils, respectively.
Conductivity was determined by the constant-head method as described by Klute
(1965). The columns were slowly saturated from below with kerosene to drive out
entrapped air. Conductivity measurements (four replicates) were obtained by keeping a
constant head of kerosene over the columns and collecting the column eluate.
2.2. Analytical procedures

Kerosene and petroleum hydrocarbons were extracted from the sand and soils in
tightly closed 25 cm3 glass flasks by adding 10 mL of Ccl, to 5 g of soil or sand. The
flasks were placed on a laboratory shaker for 24 h and then centrifuged (2500 rpm) for
10 min. An aliquot of the Ccl, was transferred to a 3 cm3 screw-cap flask with an Al
liner, and Na,SO, and Al,O, were added to remove water and humic material,
respectively. The samples were stored at 4C until analysis.
Extract aliquots (3 pL) were manually injected into a Varian 3300 gas chromatograph equipped with a flame ionization detector connected to a Merck-Hitachi D-2000
integrator and a 30 m DB-1 megabore column (i.d. 0.53 mm, film thickness 1.2 pm).
Chromatographic conditions were: 2 min at 5OC, ramp of 2/min to 12OC, and ramp
of SOC/min to 220C. The carrier gas was N,. The flow rates for N,, H,, and air were
30, 30, and 300 cm3/min, respectively.
Kerosene viscosity was measured by a Schott Gerate type 53001/01 viscometer in
a water bath at 27C. All measurements were replicated five times.

3. Results and discussion

3.1. Retention

Petroleum products can be retained by soil solids either by entrapment in soil

capillaries and pores or by sorption at particle surfaces. Physical and chemical properties
of the soil solid phase, including hydration status, texture and organic matter content,
control the degree of hydrocarbon entrapment and sorption.
3.1.1. Physical entrapment

Entrapment is a form of non-adsorption retention of nonaqueous phase liquids in

soils. The immiscible fluids (water and nonaqueous liquid) hinder each others transport

138

Fig. 1. Kerosene
1993).

P. Fine et al/Soil

residual

content

(KFX)

Technology

of soils as a function

10 (1997)

133-153

of clay and moisture

contents

(Fine and Yaron,

through the soil until a minimum saturation is reached. Nonaqueous fluids can then
become trapped as blobs or ganglia in pores in the unsaturated zone for an indefinite
time (Schwille,
1994) serving as a source of contamination which decreases in
magnitude as the nonaqueous liquid volatilizes, dissolves in water, or degrades. The
degree of soil saturation for a water-immiscible
liquid can be expressed as the
proportion of pore space occluded by a given liquid phase (van Dam, 1967; Schwille,
1981) or as the liquid content in volume per unit weight of soil (Mercer and Cohen,
1990).
The extent of trapping is determined primarily by the physical properties of the
vadose zone and the nonaqueous contaminant. Fine and Yaron (1993) and Jarsjo et al.
(1994) studied the influence of soil constituents (sand, silt, clay and organic matter) and
soil moisture content on entrapment of kerosene,measuredas keroseneresidual capacity
(KRC) in analogy to water residual capacity.
The physical retention of liquid kerosenein soil pores, or keroseneresidual capacity,
was evaluated for eleven different soils under four soil moisture regimes (oven-dry,
air-dry, 33 kPa tension and 100 kPa tension) (Fine and Yaron, 1993). KRC of the
oven-dry soils ranged from 3.5 to 18.1 mL/lOO g, and was in most casessignificantly
lower than the corresponding water retention capacity (33 kPa tension). KRC was
affected strongly by the clay content of the soil, suchthat heavy clay-rich soilshad KRC
values 1.5-2 times greater than light sandy soils (Fig. 1). KRC was also directly related
to silt and organic matter (OM) contents. Using multivariant analysis, a highly significant relationship between silt, clay, and organic matter components and KRC was
obtained. In a similar study of glacial soils, KRC was also found to vary as a function of
soil texture and organic matter content (Jarsjo et al., 1994).
When moisture content was varied, both Fine and Yaron (1993) and Jarsjo et al.
(1994) found that KRC was inversely linearly related to the moisture content and was
linearly related to soil texture (characterized by clay content) and OM content (Fig. 1).
As soil moisture content increased, the KRC decreased markedly and attained a

P. Fine et al. / Soil Technology

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139

relatively uniform, low value in all soils. It was postulated that water was strongly
retained in small soil capillaries resulting in a reduction in soil effective porosity. This
would lead to a significant reduction in both the physical entrapment of liquid
hydrocarbon in small pores and capillaries and a reduction in hydrocarbon sorption at
mineral and organic matter surfaces (e.g., Mills and Biggar, 1969; Mortland, 1970;
Chiou and Shoup, 1985; Pignatello, 1989; Mingelgrin and Prost, 1989).

3.1.2. Sorption from the vapor phase

Sorption of petroleum hydrocarbons by the soil solid phase and on different soil
constituents has been the subject of numerous studies over the years. Nathwani and
Philips (1977) studied the sorption of selected hydrocarbons from the vapor phase
(benzene, o-xylene, toluene, and n-hexadodecane) on a number of Canadian soils and
found that for concentrations between 1 and 100 ppm, hydrocarbon sorption was well
described by the Freundlich isotherm. Soils with a higher organic matter content
exhibited higher values of the distribution coefficient. Many other studies reported that
sorption of organic compounds from vapor, aqueous, and organic solvent phases onto
clay surfaces could be described by the Langmuir isotherm or more complex, composite
isotherms (Greene-Kelly, 1954a; German and Harding, 1969; Olejnik et al., 1974). The
intercalation of hydrocarbon species into expanding layer silicates is considered a
process by which some part of the interlayer water associated with the exchangeable
cations is replaced by the organic species (Theng, 1974). In dehydrated systems where
the silicate layers of a clay crystal are fully collapsed, intercalation of hydrocarbons is
either absent or proceeds only with difficulty (Greene-Kelly, 1954b). The studies of
Clementz (1976) on adsorption of heavy petroleum fractions (asphaltenes) from solution
at montmorillonite surfaces confirm these findings.
Nye et al. (1994) studied the kinetics of vapor sorption of m-xylene and n-dodecane
on oven- and air-dried Evesham clay soil and on a medium sand. Sorption equilibrium
for both hydrocarbons was reached in less than 2 h on the sand and in 40-80 h on the
clay soil (Fig. 2). m-xylene reached sorption equilibrium faster on the oven-dry
Evesham clay soil than on the air-dried clay soil. The total sorption capacity of the
air-dried clay was nearly twice that of the oven-dried clay while the sorption capacity of
the sand was relatively unaffected by its moisture content. The total sorption capacity of
the clay for m-xylene was 20 to 40 times that of the sand.
The sorption capacity of the clay soil for n-dodecane was approximately 15 times
that of the sand. The rate and total uptake of n-dodecane were equal in both the air-dried
and oven-dried sand, but the total sorbed amount in the air-dried clay was less than in
the oven-dried clay. In contrast, m-xylene sorption was greater in oven-dried sand than
air-dried sand, and far higher in air-dried clay than in oven-dried clay (Fig. 2). This
behavior can be partly explained on the basis of structurally-related
size exclusion
phenomena. The n-dodecane molecule is too large to penetrate clay interlayer spaces
and can sorb only to external surface area. In the air-dried clay, water successfully
competes for sorption sites resulting in a reduction of n-dodecane sorption compared
with oven-dried clay. In the sand, the moisture content for air-dried and oven-dried
sands are so similar that there is little or no competition for external sorption sites
between water and n-dodecane. The smaller, planar m-xylene molecule in contrast, can

140

P, Fine et

al./Soil Technology

10 (1997)

m - Xylene

133-153
n - Dodecone

Time (days 1

12

16

Time (days)

Fig. 2. Kinetics of m-xylene and n-dodecane vapor sorption by medium sand and Evesham clay soil (Nye et
al., 1994).

penetrate clay interlayers in the expanded air-dried form, while the oven-dried clay
interlayer spaces are not accessible. In dehydrated systems the silicate layers of clay
minerals are fully collapsed and the intercalation of non-polar organic liquids and gases
is either absent or proceeds only with difficulty, with sorption occurring predominantly
on external surfaces (Theng, 1974). In partly dehydrated or air-dry systems where clay
layers are slightly separated, intercalation of nonpolar organics is favored. Sorption of
m-xylene sorption in the air-dried and oven-dried sand is similar, with a small reduction
in total sorption on the air-dried sand. In this case, water may have successfully
competed for surface sorption sites with the m-xylene molecule.
Sorption isotherms for m-xylene and n-dodecane are plotted in Fig. 3 as micromoles
of compound per gram soil versus the relative vapor concentration of the compound,
P/P,. The use of P/P,, in isotherm plots to normalize the activity of each compound
with respect to its own pure state permits a direct comparison between the uptake of
different compounds. P values were measured and P, values for the compounds
studied were taken from the literature.
Slopes of the isotherms for both m-xylene and n-dodecane in the clay soil increase
with increasing P/P,,. Uptake of both compounds is strongly affected by moisture
content and by soil texture. The maximum sorption on oven-dried sand was about 10
pmol/g for m-xylene and 5 p,mol/g for n-dodecane, while on the Evesham clay soil
uptake was nearly 300 p,mol/g for m-xylene and over 100 p,mol/g for n-dodecane.
Partial hydration of the Evesham clay soil (air-dried) resulted in a reduction of
n-dodecane sorption for every P/P,. In contrast, sorption of m-xylene by the air-dried
clay soil was either equal (P/P, < 0.5) or greater (P/P, > 0.5) than for oven-dried soil.
These studies considered interactions between individual hydrocarbon species and the

P. Fine et al./Soil
Evesham

Technology

IO (1997)

clay

133-153

141

Sand

P/Pa
Fig. 3. Sorption of m-xylene
best-fit third-order
regressions

P/PO

and n-dodecane
vapors by medium sand and Evesham
through the origin (Nye et al., 1994).

clay soils. Lines

are

bulk soil or soil constituents. Petroleum products, however, are comprised of complex
mixtures of many hydrocarbons with individual components competing for sorption sites
on porous media. Only recently has the adsorption of petroleum products in the vadose
zone been studied as a function interactions and competition between individual
components (e.g., Baehr and Caropcioglu, 1987; Acher et al., 1989; Yaron et al., 1989).
Soil texture has a strong impact on the kinetics of hydrocarbon sorption from gaseous
hydrocarbon mixtures (Yaron et al., 1989; Nye et al., 1994). Vapor phase sorption of
five compounds (m-xylene, ps-cumene, n-decane, n-but.-benzene, and n-dodecane)
from a mixture by three soils with different clay and organic matter contents (Bet
Dagan: clay 12%, OM 0.5%; Gilat: clay 16%, OM 0.6%; Oxford: clay 35%, OM 7.2%)
is shown in Fig. 4 (Yaron et al., 1989). For oven-dry soils, sorption of the studied
compounds was greatest on the Gilat soil and was essentially equal in the Bet Dagan and
Oxford soils. Despite the fact that the Oxford soil has twice the clay content of the Gilat
soil, its sorptive capacity was significantly lower. This may be because sorption sites on
mineral surfaces are occluded by soil organic matter. Complementary studies of sorption
from the same hydrocarbon mixture on peat showed very low sorption capacity. In
sorption from the vapor phase, free mineral surfaces rather than organic matter control
hydrocarbon sorption. This is in contrast to sorption from the aqueous phase, where soil
organic matter content is strongly correlated with sorptive capacity (Karickhoff,
1981;
Chiou, 1989; Chin et al., 1991). In a related study it was shown that the sorption order
from the mixture (m-xylene > n-decane > ps-cumene > t-butylbenzene > n-dodecane)
corresponds to increasing boiling point and molar weight, rather than to vapor pressure
(Acher et al., 1989).
An increase in soil moisture content led to a decrease in soil sorptive capacity for all
the hydrocarbons studied (Fig. 5; Yaron et al., 1989). At a soil moisture content

142

P. Fine et al./Soil

Technology

zocyy;* ;-l,y
0

IO

20

30

10 (1997)

133-153

----

Bet Dagon
Oxford

.-.-.

Gilot

1 J&L-&y
40

IO

Time (days)

20

1
30

40

Time (days 1

Fig. 4. Sorption kinetics for hydrocarbons

from a surrounding
different soils: Bet Dagan (clay 12%, OM 0.5%); Gilat (clay
7.2%) (Yaron et al., 1989).

atmosphere of a simulated kerosene by three

16%, OM 0.6%); and Oxford (clay 35%, OM

BET XW
MOISTURE (76)
-.-.-.-

0.0
0.0
_______________-II.2
+ STANDARD DEVIATION

TIME

Fig. 5. Effect of initial soil moisture

atmosphere of a simulated kerosene

(days)

content on the kinetics of hydrocarbon

by Gilat soil (Yaron et al., 1989).

adsorption

from

a surrounding

P. Fine et al/Soil
100

m- Xylene

Technology

-Bet

10 (1997)

---.-.-.

133-153

143

Dogon
Oxford
Gilot

n - But. Benzene

Time(h)

Time (h)

Fig. 6. Desorption
of kerosene components by volatilization
from the surfaces of three oven-dried
soils as a
function of time: Bet Dagan (clay 12%. OM 0.5%); Gilat (clay 16%, OM 0.6%); and Oxford (clay 35%, OM
7.2%) (Yaron et al., 1989).

equivalent to 70% of field capacity (11%) the adsorption of hydrocarbons was almost
negligible. This behavior was also observed for the same hydrocarbon mixture by Acher
et al. (1989) and by Chiou and Shoup (1985) and Barbee and Brown (1986) for benzene
and xylene, respectively.

3.2. Volatilization
Petroleum products typically contain components with vapor pressures ranging over
several orders of magnitude. Rates of volatilization for each component will differ such
that more volatile components will diffuse out of the porous framework more rapidly
than less volatile compounds. The residual hydrocarbon mixture will thus be enriched in
less volatile components.
Desorption of kerosene components from soil surfaces to the vapor phase depends
upon the vapor pressure of each component and is affected by soil properties (Fig. 6;
Yaron et al., 1989). The highest rate of desorption was exhibited by m-xylene and the
slowest by n-dodecane. The Oxford and Gilat soils had the highest, essentially co-equal
retention capacities while the Bet Dagan soil had a significantly lower retention
capacity. Residual hydrocarbon after 7 days in the Bet Dagan soil was n-dodecane > nbutylbenzene > ps-cumene > n-decane > m-xylene. Significant hydrocarbon residues
were found in both the Oxford soil and Gilat soils.

144

P. Fine et al. / Soil Technology 10 (1997) 133-1.53

17

TIME

(dayr)

I
II
I
I

SAND

-5OLAN

17

TIME (days)
Fig. 7. Volatilization
of kerosene from the 5-15
enhanced venting. (Fine and Yaron, 1993.)

cm soil layer (in % of initial

content):

(A) free and (B)

Fine and Yaron (1993) reported the results of a study in which the volatilization of
kerosenefrom four soilswas examined as a function of natural or enhancedventing. The
soils were characterized by clay, moisture and organic matter content: dune sand, very
fine montmorillonitic clay soil with 1.6% OM (Golan), very fine montmorillonitic clay
soil with 5.1% OM (Carmel), and fine loamy soil with 2% OM (Nahal Oz) (Table 1).
Induction of an-phasetransport via enhancedventing significantly increasedthe loss of
kerosene through volatilization from all four soils (Fig. 7). Volatilization losseswere
also dependenton soil clay content, moisture status, and air permeability. This dependence was quantified by relating the lossof kerosene(LOSS as a percentageof KRC) to
clay content, hygroscopic moisture content (HYG), and air permeability coefficient
(K,). The percent loss after 17 days of enhancedventing was strongly dependenton the
air permeability:

with an R2 = 0.98. The contribution of air permeability to the correlation was clear in

P. Fine et al. /Soit

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145

o.*A
:p

0.6-&\A--------0.4
3 --l-i ------.
il
I
0.2
0

'!.\.A
. \. , N-ep.-.

----__
.*.-

.-.-.-.-.

Time(h)

40

60

120

160

200

Time (hl

Fig. 8. Evaporation
of m-xylene
(solid squares), n-dodecane
(solid circles),
and m-xylene:n-dodecane
mixtures
(32:68 open squares; 54:46 solid triangles;
84:16 open triangles).
Lines are model predictions,
symbols are actual data. The results are plotted as fraction of initial mass remaining
after time dependent
evaporation
from (A) liquid, (B) medium sand, (C) Evesham oven-dry clay, (D) Evesham air-dry clay (Nye et
al., 1994).

both the free and the enhanced venting methods. The air flux density (in m3 per
container per day) calculated for enhanced venting ranged from 0.53 & 0.02 in the
loessial soil to 2.23 k 0.25 in the sand. Increased clay content resulted in decreased
kerosene loss by volatilization, perhaps by blocking kerosene access to open voids or
because the voids themselves are smaller.
Nye et al. (1994) studied the relative volatilization of m-xylene and n-dodecane
separately and as mixtures from solution and soil (Fig. 8). The rate of volatilization of
the mixture is controlled by the ratio between its two components. As volatilization
proceeds, the decrease in m-xylene:n-dodecane ratio in the mixture led to a decrease in
the rate of evaporation of the hydrocarbon mixture. Interactions between the two
components and sorption at soil surfaces temporarily reduced the vapor phase concentration and diffusion into the gas phase. Once the system reached a steady state, however,
the final apparent steady state vapor diffusion coefficient was a function of the air-filled
porosity and was not related to properties of the soil matrix. As in the case of individual
petroleum hydrocarbon mass transfer into the atmosphere, the greatest remaining portion
of initial mass for the mixtures occurred in oven-dry Evesham clay soil, and the highest
volatilization rate occurred in a coarse sand. These results agreed with those of Mackay
and Yeun (1983), such that volatilization from a mixture of components is a function of
the vapor pressures of individual components.

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3.3. Transport
Multiphase transport of petroleum hydrocarbons in porous media is affected by the
hydraulic and physical properties of the soil as well as its hydration status. Acher et al.
(1989) showed that during liquid kerosene infiltration into a soil, there is simultaneous
but faster vapor transport creating a penetration front in advance of the liquid front. The
penetration of the hydrocarbon vapor may be two to three times greater than that of the
immiscible liquid. As the composition of the vapor phase is different from that of the
original hydrocarbon mixture (Fig. 91, soil contamination by the vapor phase will be
different from that caused by the immiscible liquid phase.
The initial soil moisture content affects the penetration of hydrocarbons both as an
immiscible liquid and as vapor in the gas phase. Liquid hydrocarbon infiltration rate and
extent in a sandy loam increased with increasing soil moisture content (Fig. 10; Acher et
al., 1989). Infiltration rate and extent for the vapor, in contrast, was inversely related to
soil moisture content. The highest rate and greatest depth of m-xylene vapor penetration
was observed in oven-dry soil (moisture content O%), with decreasing penetration rate
and depth with increasing moisture content (Fig. 11). The distribution of the less volatile
n-dodecane showed no dependence on soil moisture content (Fig. 11). The redistribution
of n-decane was very similar to that of m-xylene, while that of r-butylbenzene and of
pseudo-cumene was between that depicted by (a) and (b) in Fig. 11. In another series of
column experiments, a soil moisture content over 40% prevented the development of a
separate vapor phase. These results are similar to those of Barbee and Brown (198~3

IOOInitial

I Day

50 Days

80 60 Vapour

phase

Liquid

phase

4020 %

0 20 4060
80
100

Fig. 9. Relative
1989).

compositions

m-Xylenc
ps- Cumcna

tJ n-But.-

of simulated

p
1

kerosene

Benzen

n-oecane

n - Oodscane

and surrounding

gaseous phase (after

Yaron

et al.,

P. Fine et al./Soil

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I -

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147

content (%)
0.0

2 - 0.8
3 - 4.0
4 - 12.0

Y
of0 2 4 6 8 IO 12 I4 I6
Time (days)
Fig. 10. Penetration depth as a function of time of simulated kerosene
by initial soil moisture content: oven-dry,
0.0%; air-dry, 0.8% (Acher

in a Bet Dagan soil column

et al., 1989).

as affected

who reported that xylenes applied to a sandy loam with a moisture content close to field
capacity were retained by the soil and their movement significantly attenuated by the
presence of water in soil pores.
In additional column studies, it was shown that kerosene components moved faster
and deeper in air-dry than in oven-dry soil columns (Acher et al., 1989). This behavior
agrees with the adsorption pattern described above. The extent of redistribution with
depth was affected by the hydrocarbon properties. In the case of oven-dry soils, the
penetration of the kerosene products was in order of increasing vapor pressure, with
m-xylene exhibiting the greatest depth of penetration, and n-dodecane the least. In the

Fig. 11. Redistribution

of (a) m-xylene
and (b) n-dodecane from a simulated liquid kerosene
in Bet Dagan
soil columns with different initial moisture contents: 1, 0.0%; 2, 0.8%; 3, 12.0%. Numbers on curves represent
days after kerosene application
(Yaron et al., 1989).

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I 1 I
.t
E
2
C

Cl4

Cl3

(b)

Retention
Fig. 12. Composition

of a kerosene

Cl4

Sandy
clay

time (min 1

in soils (a) immediately,

and (b) 14 days after addition.

case of air-dried soil columns, the redistribution of kerosene components was only
slightly affected by their volatility.
Interactions between soil and nonaqueous phase liquids are affected not only by soil
texture and moisture content but by the nature of the nonaqueous liquid. The composition of a volatile organic liquid mixture (kerosene) in different soils undergoes preferential volatilization of lighter fractions as a function of clay content (Fig. 12). As the
composition of the mixture changes, the physical properties of the residual liquid also
change. The relationship between the viscosity of kerosene after volatilization and the
relative concentrations of its major components is depicted in Fig. 13 (Gerstl et al.,
1994). An increase in kerosene viscosity was accompanied by a relative increase in
heavy fractions (C13-C15) and decrease in light fractions (C9-Cl 1). Galin et al.

viscosity

0
c9

Cl0

(Pa 0 10-3)

CII

Cl2
Carbon

Fig. 13. Composition

of kerosene

Cl3

Cl4

Cl5

of viscosity

(Gerstl

et al., 1994).

number

as a function

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1.2
1.4

Viscosity

Fig. 14. Kerosene

conductivity

1.6

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133-153

149

2.0

(Pa s 10m3)

as a function

of viscosity

(Gerstl

et al., 1994).

(1990b) showed that the increase in viscosity due to the change in kerosene composition
was not accompanied by changes in its surface tension and by only small changes in its
density (from 0.805 to 0.819 g ml-). An increase in viscosity from 1.32 to 1.96 lop3
Pa s led to a 28% decrease in kerosene conductivity in sand, a 76% decrease in loam
soil, and an 83% decrease in clay soil (Fig. 14). Intrinsic permeability for the three soils
was calculated by:
K= kpgp-
where p is fluid density (g ml-),
g is acceleration due to gravity (m/s) and p, is
dynamic viscosity of the fluid (Pa s- 1. The measured kerosene intrinsic permeability of
the sand was unaffected by changes in viscosity, while in the loam and clay soils,
intrinsic permeability decreased as viscosity increased (Fig. 15)
The rate of flow of a fluid through a pore is proportional to the fourth power of its
diameter (Poiseuilles law), so that even a small change in the pores effective diameter
may have a significant effect on permeability. Effective porosity may have been reduced
by the presence of hydrocarbon films on soil surfaces forming an immobile region
analogous to that of immobile water in natural soil-water
systems.
A second mechanism which can reduce the intrinsic permeability of a medium is the
swelling of expandable components such as clays. No changes in intrinsic permeability
were detected in a non-swelling medium (sand) upon volatilization of lighter components (Galin et al., 1990a; Galin et al., 1990b; Gerstl et al., 19941, while intrinsic
permeability decreased in swelling media (loam and clay) (Gerstl et al., 1994). Thus,
swelling or dispersion of clay in the changing solvent mixture may have been responsible for decreases in intrinsic permeability.
Swelling and contraction of expandable clays in contact with solvents are sometimes
explained by the diffuse double layer (DDL) theory which predicts an increase in the

P. Fine et aL/Soil

150

u
.,z
is
2

0.2-

--.--

Theorctkol
Sand

--o--

Loan

--m-0

1.3

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I

1.4

1.5
Viscosity

10 (1997)

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1.6

I.?

1.8

1.9

2.0

(Po s (OS31

Fig. 15. Kerosene conductivity

(relative to that of the original kerosene) as a function of viscosity. The solid
line was calculated with the experimentally
determined
values of the viscosity and density of the kerosene
(Gerstl et al., 1994).

equilibrium distance between clay plates as pore fluid dielectric constant (E) increases
(Barshad, 1952; Norrish, 1954; Olejnik et al., 1974; Murray and Quirk, 1982). However,
Graber and Mingelgrin (1994) showed that regular solution theory is more successful in
describing clay swelling in solvents than is the DDL theory, in accordance with the
suggestion that swelling is controlled by solvation rather than changes in the DDL
(MacEwan, 1948; Low and Margheim, 1979; Low, 1980; Low, 1981). The regular
solution theory is a thermodynamic model originally developed to describe miscibility in
binary, small molecule, non-polar systems (Hildebrand et al., 1970). It is also successfully applied to swelling or dissolution of polymers in solvents. Graber and Mingelgrin
(1994) extended the regular solution theory to clay swelling in solvents by way of
analogy to polymer swelling.
Permeability of a porous medium can either decrease or increase as a result of
swelling depending on the composition and structure of the porous medium. In a system
of uniform spheres of radius R, intrinsic permeability is proportional to R2. As R
increases, intrinsic permeability also increases. If interstices between the spheres are
filled with cuboids and the volume of each cuboid increases (for example, sand and
clay), the intrinsic permeability of the system will decrease.
Gerstl et al. (1994) reported that in a clay soil, volatilization of kerosene was
accompanied by a decrease in intrinsic permeability. During volatilization, the dielectric
constant of the mixture remained unchanged. Thus, by the DDL theory, the observed
decrease in intrinsic permeability cannot be attributed to swelling. However, the
solubility parameter of the mixture did increase. This, according to the work of Graber
and Mingelgrin (19941, can result in clay swelling and the observed reduction in
intrinsic permeability.

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151

4. Conclusions
Petroleum products commonly consist of complex mixtures of volatile hydrocarbons
with different vapor pressures. In soils contaminated by petroleum products, the
volatilization of light hydrocarbon fractions will lead to changes in the viscosity and
density of the residual nonaqueous liquid. These changes affect transport characteristics
of the residual liquid. Changes in residual hydrocarbon composition that occur upon
volatilization may also result in irreversible changes in the transport characteristics of
the porous media by virtue of interactions between the liquid and the matrix. Interactions
resulting in swelling or shrinking of clays, for example, can alter the intrinsic permeability of the porous medium. Both vapor phase and nonaqueous liquid phase transport can
contribute to soil contamination. As soil moisture content decreases, vapor phase
transport increases and soil retention of hydrocarbons increases. With increasing moisture content, vapor phase transport and soil retention by entrapment or sorption
decreases, resulting in an increase in transport of nonaqueous phase liquid. Contaminants transported in the vapor phase will differ from those transported in the liquid
phase.

Acknowledgements
The reported results were obtained with the support of the Ministry of Science and
Technology (MOST), Israel, and the Bundeministerium fur Forschung und Technologie
(BMFT), Germany.

References
Acher, A., Boiderie, P. and Yaron, B., 1989. Soil pollution by petroleum products. I. Multiphase
migration of
kerosene components in soil columns. J. Contam. Hydrol., 4: 333-345.
Baehr, A.L. and Caropcioglu,
M.Y., 1987. A compositional
multiphase model for groundwater
contamination.
2. Numerical
model by petroleum products. Water Resour. Res., 33: 201-213.
Barbee, G.C. and Brown, K.W., 1986, Movement
of xylene through unsaturated
soils following
simulated
spills. Water Air Soil Pollut., 29: 321-333.
Barshad, I., 1952, Factors affecting the interlayer expansion of vermiculite
and montmorillonite
with organic
substances. Soil Sci. Sot. Am. J., 16: 176-182.
Calabrese, E.J. and Kostecki, P.T., ed., 1988. Soils Contaminated
by Petroleum. John Wiley and Sons, New
York, NY, 457 pp.
Chin, Y.P., Weber W.J. and Chiou C.T., 1991. A thermodynamic
partition model for binding of nonpolar
organic compounds by organic colloids and implications
for their sorption to soils and sediments. In: ed.
R.A. Baker, Organic Substances and Sediments in Water, Vol. 1, Humics and Soils. Lewis Publishers,
USA, pp. 251-273.
Chiou, C.T., 1989. Theoretical considerations
of the partition uptake of nonionic organic compounds by soil
organic matter. In: ed. B.L. Sawheny and K. Brown, Reaction and Movement
of Organic Chemicals in
Soils. SSSA Special Publication
No. 22, Ed. Madison, WI. Soil Sci. Sot. Am., l-30.
Chiou, C.T. and Shoup T.D., 1985. Soil sorption of organic vapors and effects of humidity
on sorptive
mechanism and capacity. Environ. Sci. Technol., 19: 1196-1200.
Clementz, D.M., 1976. Interactions of petroleum heavy leads with montmorillonite.
Clay Miner., 24: 312-319.

152

P. Fine et al./Soil

Technology

10 (1997)

133-153

Fine, P. and Yaron, B., 1993. Outdoor experiments

enhance volatilization
by venting of kerosene components
from soil. J. Contam. Hydrol.,
12: 355-374.
Galin, T., Gerstl, Z. and Yaron, B., 1990a. Soil pollution by petroleum products. III. Kerosene stability in soil
columns as affected by volatilization.
J. Contam. Hydrol.,
5: 375-385.
Galin, T., McDowell,
C. and Yaron, B., 1990b. The effect of volatilization
on the mass flow of a nonaqueous
pollutant liquid mixture in porous media: experiments
with kerosene. J. Soil Sci., 41: 631-641.
German, W.L. and Harding, D.A., 1969. The adsorption of aliphatic alcohols by montmoxillonite
and kaolinite.
Clay Miner., 8: 213-227.
Gerstl, Z., Galin, T. and Yaron, B., 1994. Mass flow of a volatile organic liquid mixture (VOLM)
in soils. J.
Environ. Qual., 23: 487-493.
Graber, E.R. and Mingelgrin,
U., 1994. Clay swelling and regular solution theory. Environ. Sci. Technol., 28:
2360-2365.
Greene-Kelly,
R., 1954a. Sorption of aromatic organic compounds by montmorillonite.
Part I. Orientation
studies. Trans. Faraday Sot., 51: 412-424.
Greene-Kelly,
R., 1954b. Sorption of aromatic organic compounds by montmorillonite.
Part II. Packing studies
with pyridine. Trans. Faraday Sot., 51: 425-430.
Hildebrand,
J.H., Prausnitz,
J.M. and R.L. Scott, 1970. Regular and Related Solutions.
Van Nostrand
Reinhold, New York.
Jarsjo, J., Destouni, G. and Yaron, B., 1994. Retention and volatilization
of kerosene laboratory
experiments
on glacial and post glacial soils. J. Contam. Hydrol.,
17: 167-185.
Karickhoff,
S.W., 1981. Semi-empirical
estimation of sorption of hydrophobic
pollutants on natural sediments
and soil. Chemosphere,
10: 833-846.
Klute, 1965. ????
Kostecki, P.T. and Calabrese, E.J., ed., 1991. Hydrocarbon
Contaminated
Soils and Ground Water. Lewis
Publishers Chelsea, Michigan,
354 pp.
Low, P.F. and Margheim,
J.F., 1979. The swelling of clay: I. Basic concepts and empirical equations. Soil Sci.
See. Am. J., 43: 473-481.
Low, P.F., 1980. The swelling of clay: II. Montmorillonites.
Soil Sci. Sot. Am. J., 44: 667-676.
Low, P.F., 1981. The swelling of clay: III. Dissociation
of exchangeable
cations. Soil Sci. Sot. Am. J., 45:
1074-1078.
MacEwan,
D.M.C.,
1948. Complexes
of clays with organic compounds.
I. Complex
formation
between
montmorillonite
and halloysite and certain organic liquids. Trans. Faraday Sot., 44: 349-367.
Mackay,
D. and Yeun, T.K., 1983. Mass transfer coefficient
correlations for volatilization
of organic solutes
from water. Environ. Sci. Technol., 13: 211-212.
Mercer, J.W. and Cohen, R.M., 1990. A review of immiscible fluids in the subsurface. J. Contam. Hydrol., 6:
107-163.
Mills, A.C. and Biggar, J.W., 1969. Solubility-temperature
effect on the adsorption of gamma and beta-BHC
from aqueous and hexane solutions by soil materials. Soil Sci. Sot. Am. Proc., 33: 210-216.
Mingelgrin,
U. and Prost, R., 1989. Surface interactions of toxic organic chemicals with minerals. In: ed. Z.
Gerstl, Y. Chen, U. Mingelgtin,
B. and Yaron, B., Toxic Organic Chemicals in Porous Media. SpringerVerlag, Berlin, pp. 91-135.
Mortland,
M.M., 1970. Clay-organic
complexes and interactions.
Adv. Agron., 22: 75-l 17.
Murray,
RX and Quirk, J.P., 1982. The physical swelling of clays in solvents. Soil Sci. Sot. Am. J., 46:
865-868.
Nathwani,
J.S. and Philips, C.R., 1977. Adsorption-desorption
of selected hydrocarbons
in crude oil and soils.
Chemosphere,
4: 157-162.
Norrish, K., 1954. The swelling of montmorillonite.
Discuss. Faraday Sot., 18: 120-134.
Nye, P.H., Yaron, B., Galin, T. and Gerstl, Z., 1994. Volatilization
of a multi-component
liquid through dry
soils. Soil Sci. Sot. Am. J., 58: 269-277.
Olejnik, S., Posner, A.M. and Quirk, J.P., 1974. Swelling of montmorillonite
in polar organic liquids. Clays
Clay Miner., 22: 361-365.
Pignatello, J.J., 1989. Sorption dynamics of organic compound in soils and sediments. In: ed. B.L. Sawhney
and K. Brown, Reactions and Movement
of Organic Chemicals in Soils. SSSA Special Publication
No. 22:
45-81.

P. Fine et al/Soil

Technology

10 (1997)

133-153

153

Schwille,
F., 1981. Groundwater
pollution
in porous media by fluids immiscible
with water. Sci. Total
Environ., 21: 173-185.
Schwille,
F., 1994. Migration
of organic fluids immiscible
with water in the unsaturated
zone. In: ed. B.
Yaron, G. Dagan, and J. Gold&mud,
Pollutants in Porous Media. Springer-Verlag,
Berlin, pp. 27-47.
Theng, B.G.G., 1974. The Chemistry
of Clay Organic Residues. Hilger, London, UK, 343 pp. 245.
van Dam, J., 1967. The migration
of hydrocarbons
in a water-bearing
stratum. In: ed. P. Hepple, The Joint
Problems of the Oil and Water Industries. Inst. of Petroleum, London, UK, pp. 55-96.
Yaron, B., 1989. On the behavior of petroleum hydrocarbons
in the unsaturated zone: Abiotic aspects. Ecol.
Stud., 73: 21 l-230.
Yaron, B., Sutherland,
P., Galin, T. and Acher, A.J., 1989. Soil pollution
by petroleum
products.
II.
Adsorption-desorption
of kerosene vapors on soils. J. Contam. Hydrol., 4: 342-358.