Professional Documents
Culture Documents
TECHNOLOGY
ELSEVIER
18 January
Center,
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;
e-mail:
134
Technology
10 (1997)
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.
(wt%)
clay
silt
SSA
sand
(after
(m/g)
135
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):
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
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
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.
P. Fine et al./Soil
Technology
10 (1997)
133-153
137
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.
138
Fig. 1. Kerosene
1993).
P. Fine et al/Soil
residual
content
(KFX)
Technology
of soils as a function
10 (1997)
133-153
contents
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
IO (1997)
133-153
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).
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).
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
BET XW
MOISTURE (76)
-.-.-.-
0.0
0.0
_______________-II.2
+ STANDARD DEVIATION
TIME
(days)
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
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.)
content):
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
Technology
10 (1997)
133-153
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.
146
Technology
10 (1997)
133-153
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
Yaron
et al.,
P. Fine et al./Soil
Technology
10 (1997)
Moisture
I -
133-153
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
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
148
Technology
10 (1997)
133-153
I 1 I
.t
E
2
C
Cl4
Cl3
(b)
Retention
Fig. 12. Composition
of a kerosene
Cl4
Sandy
clay
time (min 1
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
of kerosene
Cl3
Cl4
Cl5
of viscosity
(Gerstl
et al., 1994).
number
as a function
P. Fine et al./Soil
Technology
1.2
1.4
Viscosity
conductivity
1.6
10 (1997)
I.8
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
Technology
Cloy
I
1.4
1.5
Viscosity
10 (1997)
133-153
1.6
I.?
1.8
1.9
2.0
(Po s (OS31
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.
P. Fine et al/Soil
Technology
10 (1997)
133-153
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.
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