Klusman, R. W., and M. A.

Saeed, 1996, Comparison of light hydrocarbon

microseepage mechanisms, in D. Schumacher and M. A. Abrams, eds.,
Hydrocarbon migration and its near-surface expression: AAPG Memoir 66,
p. 157168.
Chapter 12
Comparison of Light Hydrocarbon
Microseepage Mechanisms
Abstract
Surface geochemistry applied to hydrocarbon exploration has gained little acceptance due to the lack of a sat-
isfactory mechanism for vertical migration that is plausible and explains all observations. Acceptance of surface
geochemistry is also hampered by a widely held belief that reservoirs do not leak. A satisfactory mechanism
must apply in a wide variety of geologic environments and must be verified by laboratory and field observa-
tions. Three mechanisms are proposed for vertical migration of light hydrocarbons: diffusion, transport in aque-
ous solution, and buoyancy of microbubbles.
Diffusion fails to explain the rapid disappearance of surface anomalies after production from a reservoir
begins. Diffusion is sufficiently rapid to dissipate gas reservoirs quickly in the geologic sense. As a vertical
migration mechanism, it also cannot account for the resolution observed in surface anomalies. Diffusion as a
mechanism for primary migration of hydrocarbons from source rocks and as a transport mechanism in the near-
surface unsaturated zone have been demonstrated. Solubilities of light hydrocarbons in water are low at ambi-
ent temperatures, but increase dramatically with increasing temperatures at depth in basins. Transport with
water, either in solution or as a separate hydrocarbon phase, is important in secondary migration. Computer
modeling of the process using finite-difference techniques fails to explain the observed resolution and rapid dis-
appearance of surface anomalies.
We favor the vertical migration mechanism of displacing water by ascending gas bubbles, that is, the buoy-
ancy of microbubbles. Computer modeling of this mechanism does explain surface observations. The close cor-
respondence of surface anomalies with surface projections of a reservoir and the rapidly disappearing surface
anomalies after the start of production are predicted by this model.
INTRODUCTION
The acceptance and use of surface geochemistry in the
past 60 years has been limited by two major problems.
The first is a two-part problem: direct observation of the
microseepage process and development of a defensible
theory about how microseepage occurs. The second prob-
lem is the complexity of the secondary reactions occur-
ring in light hydrocarbons that are undergoing
microseepage. These reactions, dominated by oxidation
in the upper part of the sedimentary section or in the soil
column, can result in many changes and alterations in the
near surface. These manifestations are the basis of indirect
surface exploration techniques (Klusman, 1993).
We focus on the microseepage process itself and the
more prominent mechanisms for the transport of light
hydrocarbons from the level of the reservoir to the sur-
face. Each proposed mechanism is discussed along with
the evidence for and against it. To be favored, a mecha-
nism must apply in most sedimentary environments. The
favored mechanism must also explain most of the empir-
ical observations that have accumulated during the 60+
years of surface exploration.
The existence of microseepage is supported by a large
amount of empirical evidence. Foremost are (1) an
increase in nonmethane light hydrocarbons as a reservoir
is approached during the mud logging of many wells; (2)
an increase in C
2
/C
1
, C
3
/C
1
, and C
4
/C
1
ratios in soil gas
over hydrocarbon reservoirs; (3) sharp lateral changes in
these ratios at the edges of the surface projections of
hydrocarbon reservoirs; (4) the similarity of stable carbon
isotopic ratios for methane in soil gases to those found in
157
Ronald W. Klusman
Department of Chemistry and Geochemistry
Colorado School of Mines
Golden, Colorado, U.S.A.
Mahyoub A. Saeed
Faculty of Science
University of Sanaa
Sanaa, Republic of Yemen
underlying hydrocarbon reservoirs; and (5) undetectable
amounts of
14
C in soil gas hydrocarbons and secondary
oxidation products, suggesting ancient sources of carbon.
The rate of transport of light hydrocarbons from the
reservoir to the surface is hypothesized to be rapid, on the
order of months or a few years, and not requiring signifi-
cant geologic time (MacElvain, 1969). Evidence for rapid
transport is primarily from the common observation that
a light hydrocarbon soil gas anomaly disappears after ini-
tiation of production from a reservoir (Horovitz, 1969).
Light hydrocarbons are also observed to increase in a soil
gas over pressurized demand gas storage reservoirs
(Coleman et al., 1977; Araktingi et al., 1982). Hydro-
carbons observed in soil gas over storage reservoirs have
stable carbon isotope compositions similar to that of the
reservoired gas (Coleman et al., 1977). This frequent
observation of rapid transport may be the most critical for
a hypothesized mechanism to predict adequately.
We consider three mechanisms for the migration of
light hydrocarbons from reservoirs to the surface: (1) dif-
fusion, (2) transport in solution in ascending water, and
(3) buoyancy of microbubbles rising through a water-sat-
urated sedimentary column.
MECHANISMS FOR LIGHT
HYDROCARBON MICROSEEPAGE
Transport of Hydrocarbons by Diffusion
Diffusion was one of the original mechanisms cited as
being responsible for microseepage (Stegena, 1961).
Diffusion rates through water-saturated pore space have
been calculated but not directly measured in the environ-
ment of a hydrocarbon reservoir. Buckley et al. (1958)
measured the concentration of dissolved light hydrocar-
bons in formation waters and found that high concentra-
tions were localized adjacent to known petroleum and
gas reservoirs. This suggests that diffusion controlled
transport has not moved dissolved gases appreciable dis-
tances. Diffusion has been directly measured, and a satis-
factory theory developed for gas transport in soil
columns, above the saturated zone.
Stegena (1961) applied Ficks second law to the diffu-
sion of hydrocarbons in a sedimentary column. The
change in concentration with respect to time is
(1)
where D is the coefficient of diffusion and C is the con-
centration. is the del operator, a short-hand symbol
for the partial derivative of the variable that follows, in
this case concentration C. This partial derivative is with
respect to the change in concentration in three dimen-
sions, x, y, z. Only diffusion in the vertical direction is of
primary concern in this discussion. We assume that reser-
voirs fill instantly, and thereafter gases lost by diffusion
are continually replaced from source rocks. The one-
dimensional equation for vertical migration through a
plane at the top of the reservoir is
(2)
Integration of equation 2 as shown by Stegena (1961) is
(3)
Equation 3 allows calculation of the concentration of the
gas dissolved in the pore water, C
tz
, at a depth z, at time t,
between z = 0 and z = h. The concentration of the gas in
the reservoir must remain constant at C
0
.
Stegena (1961) estimated diffusion coefficients for
methane to be 10
10
to 10
12
m
2
/sec. Stegenas calculation
indicates that a steady-state concentration of methane
would be achieved at the surface only after hundreds of
millions of years, even for a relatively shallow reservoir at
1000 m. Calculated flux rates for methane to the surface
are about 2 g/m
2
/100 m.y. This exceedingly slow trans-
port rate contrasts with measured methane flux rates at
the surface in sedimentary basins on the order of
0.00.002 g/m
2
/day (Jakel and Klusman, 1995).
Leythaeuser et al. (1980) measured diffusion rates for
light hydrocarbons in shale cores from a thermally
mature, hydrocarbon-rich shale in Greenland. The origi-
nal weathered surface was planed off by glaciation, and
the section is presently in permafrost. This suggests that
microbial consumption of hydrocarbons was minimal.
Ice retreat began about 6000 years ago, allowing hydro-
carbon diffusion from the shale to the atmosphere.
Hydrocarbon concentrations in pore ice were constant
below 8 m depth, which Leythaeuser et al. (1980) defined
as C
0
. The concentration at the surface was assumed to be
zero, even though this is not equal to the atmospheric con-
centration (Warneck, 1988). Figure 1 shows the distribution
of ethane and n-butane concentrations in the rock matrix of
the core. Initial estimated concentrations C
0
from Figure 1
were 3.1 ng ethane/g rock and 165 ng n-butane/g rock.
The diffusion coefficients were calculated by Leythaeuser
et al. (1980) at 6.4 10
11
m
2
/sec for ethane and 3.2 10
11
m
2
/sec for n-butane. Calculated flux rates were about 1
g/m
2
/year for ethane and 0.1 g/m
2
/year for pentane. The
diffusion rates for light hydrocarbons found by
Leythaeuser et al. (1980) are similar in magnitude for the
C
2
C
5
hydrocarbons. Extrapolation to methane suggests a
flux for methane similar to that of ethane. This flux rate is
comparable to that found by Jakel and Klusman (1995) for
methane in sedimentary basins of temperate climates.
Leythaeuser et al. (1982) estimated the time required to
fill a gas reservoir and the time required to empty a reser-
voir by diffusive loss. They focused on the Harlingen gas
C C
z
h n
n h Dt
n z
h
tz
n
n
+

'

( )
[ ]

_
,

0
1
2 2 2
2 1

( )
exp / sin

C
t
D
C
z

2
2

C
t
D C
158 Klusman and Saeed
field in The Netherlands. They estimated the half-life of
this gas field to be 4.5 m.y., by diffusive loss through a cap
rock, if the gas were not replenished from a source.
Krooss et al. (1992a) reevaluated the calculations of
Leythaeuser et al. (1982) and suggested that the model
was too simple and did not account for the equilibration
between methane in the gas phase and dissolved
methane in the water-saturated cap rock. Krooss et al.
modified equation 3 to calculate only vertical total flux, Q,
into a cap rock:
(4)
where h is now the thickness of the cap rock. For t,
equation 4 becomes
(5)
To calculate loss of one-half of a reservoired gas, equa-
tion 5 was modified by Krooss et al. (1992a) as follows:
(6)
which is rearranged to solve for t
1/2
:
(7)
Krooss et al. (1992a) gave the cap rock thickness, h, as 390
m, with D as 2.12 10
10
m
2
/sec, Q
1/2
as 173.9 kg
CH
4
/m
2
in the cap rock, and t
1/2
as 70 m.y.
This is complicated by two factors. Once the methane
passes the cap rock, it must traverse the overlying sedi-
mentary column, which will presumably have a higher
permeability than the cap rock. Therefore, the traverse of
this part of the section will be more rapid. Also, if the
adsorptive sites in the overlying section are not saturated,
migrating gas will be removed until adsorbing sites are
saturated. Applied to surface exploration, these factors
can be ignored, if it is assumed the reservoir has existed
for sufficient time for methane and light hydrocarbons to
have traversed the cap rock and the overlying sedimen-
tary column and to have saturated the sites capable of
adsorbing methane and light hydrocarbons.
Nelson and Simmons (1992) criticized the Krooss et al.
(1992a) calculations, and Krooss et al. (1992b) replied.
Nelson and Simmons suggested that the value for Dmust
be an effective Dthat incorporates porosity, permeability,
and tortuosity terms. They calculated the value for t
1/2
to
be 11.5 m.y. for the Harlingen gas reservoir. Nelson and
Simmons (1992) also considered the effect of temperature
on the diffusion coefficient and of salinity on the viscosi-
ty of water. With a cap rock temperature of 70C and 3.6
wt. % salinity, Nelson and Simmons calculated t
1/2
to be
4.4 m.y., which was essentially the same as the original 4.5
m.y. given by Leythaeuser et al. (1982). Krooss et al.
(1992b) reiterated that the original assumptions about
porosity effects on the value for the diffusion coefficient
were correct and stated that the effect of temperature on
Dwould be addressed in a future publication.
Nelson and Simmons (1995) estimated diffusive losses
of methane and ethane for the McClave gas field on the
Las Animas Arch in southeastern Colorado. They includ-
ed the effect of temperature on the diffusion coefficient
and the effect of salinity on water viscosity. The cap rock
is shale, with an estimated porosity of 5%, and the entire
methane volume in the reservoir must be replaced from a
source (by catagenesis) every 2.2 m.y. and ethane every
5.3 m.y. For a simulated porosity of 10% in the overlying
t
Q
hC
h D
1 2
1 2
0
2
1
3
/
/
/

_
,

Q
hC
Dt
h
1 2
0
1 2
2
1
3
/ /
+
Q t
hC
Dt
h
( )
0
2
1
3
+
Q t
hC
Dt
h n
Dn t h
n
( )
exp /
0
2 2 2
1
2 2 2
2 1
1 +
( )
[ ]

Chapter 12Comparison of Light Hydrocarbon Microseepage Mechanisms 159
Figure 1Computed (dashed lines) and measured (solid
lines) concentration versus depth trends for ethane and n-
butane from corehole E in CampanianMaastrichtian
shale, Niaqorssuaq, West Greenland. Initial concentra-
tions, C
0,
used for calculation of diffusion coefficients for
ethane and n-butane were 3.1 and 165.0 ng/g, respectively
(indicated by arrows). (From Leythaeuser et al., 1980.
Reprinted with permission from Nature, v. 284. Copyright
1980 Macmillan Magazines Limited).
shale, the replacement time in the McClave field was cal-
culated by Nelson and Simmons (1995) as 0.48 m.y. for
methane and 1.2 m.y. for ethane.
Krooss et al. (1992a) calculated a total of 347.8 kg
CH
4
/m
2
under the cap rock of the Harlingen gas reser-
voir. Using the 4.4-m.y. value of Nelson and Simmons
(1992) as the half-life of the reservoir and assuming a lin-
ear rate of loss, Nelson and Simmons calculated the aver-
age flux through the cap rock as 0.11 mg CH
4
/m
2
/day.
Nelson and Simmons (1995) calculated fluxes from the
McClave field for methane and ethane. Using the 5%
porosity value for the cap rock, the flux for methane was
0.007 mg/m
2
/day and at 10% porosity the flux was 0.03
mg/m
2
/day. The calculated ethane flux was about 0.1
that of methane. It should be emphasized that the calcu-
lated losses would be a first-order decay process propor-
tional to the amount present, and the loss would not be
linear with respect to time unless the reservoir were
maintained by secondary migration or catagenesis. The
fluxes of other light hydrocarbons would be less, but
when the adsorptive capacity of the overlying sedimen-
tary column was exceeded, measurable concentrations
could be observed at the surface.
The changes in concentration in a flux chamber at the
surface for methane are within the realm of detection,
allowing calculation of flux rates. This requires that the
methane reach the surface without being consumed by
methanotrophic bacteria. A single flux determination
would not be adequate to determine low rates, just as a
single soil gas measurement would not reliably detect a
subsurface reservoir. Measured fluxes of 02 mg
CH
4
/m
2
/day given by Jakel and Klusman (1995) are in
this order of magnitude. We must emphasize that
methanotrophic bacteria in the soil column do consume
methane and light hydrocarbons. The result is apparent
negative fluxes. That is, methane is removed from the
atmosphere as the soil acts as a sink for methane.
Negative methane fluxes are commonly determined for
soils of temperate climates, particularly in areas not
underlain by sedimentary basins with hydrocarbon
potential or basins not actively generating hydrocarbons
in the subsurface. There is currently not enough known
about light hydrocarbon fluxes to effectively use such
measurements in surface prospecting. Significant positive
fluxes of methane do occur in wet environments, inde-
pendent of underlying geology, due to methanogenesis.
Thomas and Clouse (1990a,b,c) determined diffusion
coefficients for heavier hydrocarbons. Using C
15
as a
model compound, a diffusion coefficient, D, of 5.7 10
11
m
2
/sec was determined for migration through a kerogen
layer on micritic sediments. Whelan et al. (1984) deter-
mined diffusion coefficients for black shales as 1.7 10
12
,
2 10
12
, 2.6 10
12
m
2
/sec for n-pentane, n-hexane, and
n-heptane, respectively. With these lower diffusion coeffi-
cients and greater adsorption capacities, we expect that
heavier hydrocarbons will not move at appreciable rates
from reservoirs because gasoline-range hydrocarbons are
retained for much longer times than are methane and
other gaseous hydrocarbons.
The previous discussion suggests that if diffusion were
a primary mechanism of vertical migration, it should be
possible to detect elevated concentrations of methane and
light hydrocarbons in soil gases above reservoirs that are
undergoing microseepage. That is, diffusion as a trans-
port mechanism would not preclude the use of surface
geochemistry for exploration. However, the response at
the surface to a pressure decrease in a reservoir associat-
ed with production would not be detected in the short
time frame often seen in surface geochemical data
(Horovitz, 1969). The effects of nonvertical dispersion
must also be considered, which may not allow an ade-
quate explanation of the sharp definition observed for
many surface anomalies (Rice, 1986).
Light hydrocarbon transport calculated by equations 3
and 4 needs to be incorporated into a computer model of
the diffusion process in order to assess the interactions of
the many parameters. Krooss et al. (1992a, b) and Nelson
and Simmons (1992, 1995) calculated the loss of gas
through the cap rock. Since this gas is no longer recover-
able, it is not of economic interest. To test a hypothesis of
diffusion as a vertical migration mechanism and to apply
it to surface geochemical exploration, diffusion through
the entire sedimentary column must be considered.
Layered sedimentary columns must be incorporated for
each modeled layer, with each stratum having a specific
value for the diffusion coefficient. Also, the change in the
diffusion coefficient with temperature in response to the
geothermal gradient and the change in salinity as it
affects the viscosity of pore water must be considered.
Furthermore, the equations should be extended to three
dimensions, rather than one dimension, to account for
dispersion in the horizontal direction and lateral migra-
tion of connate water. Only then can a more thorough
understanding of the role of diffusion in vertical migra-
tion be determined.
Transport of Hydrocarbons by Water
Transport of hydrocarbons by water dissolved in
ascending water is a second possible mechanism for the
transport of hydrocarbons. The solubilities of hydrocar-
bons and of various petroleum fractions have been mea-
sured by Price (1976) and McAuliffe (1979). The aqueous
solubility is relatively constant for ethane through
n-butane, then decreases rapidly with increasing carbon
number from i-butane through C
12
; then the rate of
decrease in solubility is much less for heavier hydrocar-
bons (McAuliffe, 1979). Table 1 lists the solubility of the
light hydrocarbons from methane through n-octane at
25C. Water solubilities of individual hydrocarbons and
petroleum fractions increase rapidly with increasing tem-
perature (Price, 1976). Figure 2 shows that steeply increas-
ing solubilities are particularly evident for the lighter
alkanes and lighter distillation fractions.
The removal of hydrocarbons from the ascending
water must be considered. In the formation where a
hydrocarbon is reservoired, the decreased solubility with
increased salinity can be invoked as a removal mecha-
160 Klusman and Saeed
nism. The well-known salting-out of dissolved molec-
ular species estimated using the Setchenow relationship
may be a suitable mechanism for separating out a hydro-
carbon phase. Price (1976) demonstrated decreasing
hydrocarbon solubilities with increasing salinity. Jones
(1984) demonstrated secondary migration of hydrocar-
bons by a combination of solution and two-phase trans-
port. Solubilization of liquid hydrocarbons in a gas phase
was described by Neglia (1979) and would facilitate sec-
ondary migration.
For vertical migration and its application in surface
geochemistry, hydrodynamics must be considered (Tth,
1988; Rostron and Tth, this volume). Connate water in
the sediments, meteoric water added at the margins of
the basin, and structural water derived from the conver-
sion of smectite clays to illite all contribute to the source
of ascending fluids for two-phase transport. With increas-
ing depth of burial, temperature and pressure increases,
resulting in fluid volume increases (Magara, 1978).
Spencer (1987) suggested that generation of hydrocar-
bons with increasing depth and temperature adds hydro-
carbons to the fluid phase, further increasing pressure.
Bethke (1985) showed a schematic of water flow in a
subsiding basin (Figure 3). In the absence of faults, the
flow is primarily lateral through permeable layers.
Vertical flow becomes more important if the ratio of ver-
tical to horizontal path lengths becomes less than the ratio
of vertical to horizontal permeabilities. Figure 3 shows
horizontal flow velocities at about two orders of magni-
tude greater than vertical velocities. If faulting has
occurred or if high potential gradients are present (bot-
tom, Figure 3), there may be significant vertical flow.
Advection and hydrodynamic dispersion must be
considered. In the transport of hydrocarbons by water,
advective or bulk vertical transport of hydrocarbons by
water is required to be effective for surface exploration.
Evaporative loss may occur as the fluid approaches the
surface, and light hydrocarbons would partition into the
gas phase according to Henrys law. The dispersion term
would decrease maximum concentrations and decrease
resolution at the boundaries of anomalies. Tortuosity of
the sediment and transport by gaseous diffusion above
the water table would also reduce resolution in a surface
anomaly (Devitt et al., 1987; Krooss et al., 1992b; Nelson
and Simmons, 1992, 1995). Transport of light hydrocar-
bons in the gas phase above the water table is primarily
by diffusion, modified by complex meteorologic and sea-
sonal variables (Klusman, 1993).
The transport of a single hydrocarbon molecule due to
advection and dispersion can be written as follows (Bear,
1979):
(8)
where Q is the hydrocarbon flux (per liter, or L
1
), V the
velocity of water (L/sec), the water content (L), D
t
the
Q C V D C
t

[ ]
( )
Chapter 12Comparison of Light Hydrocarbon Microseepage Mechanisms 161
Table 1Solubility of Light Hydrocarbons in Water
at 25C
a
Solubility
Hydrocarbon (ppm by weight)
Methane 24.4
Ethane 60.4
Propane 62.4
n-Butane 61.4
i-Butane 48.9
n-Pentane 38.5
n-Hexane 9.5
n-Heptane 2.93
n-Octane 0.66
a
From McAuliffe (1979).
Figure 2(a) Aqueous solubilities of second (DF2,
132193C), third (DF3, 193232C), fourth (DF4,
232316C), and fifth (DF5, 316371C) distillation fractions
of Ghawar Arabian crude oil as a function of temperature
at the pressure of the system. (b) Aqueous solubility of
pentane (C
5
), hexane (C
6
), heptane (C
7
), octane (C
8
), and
nonane (C
9
) as a function of temperature at the pressure
of the system. (From Price, 1976.)
diffusion coefficient, and Cthe concentration of dissolved
hydrocarbon. If there are no chemical reactions resulting
in production or consumption of the light hydrocarbons
and no adsorption, or if the adsorption sites are already
saturated, the mass balance for a dissolved hydrocarbon
becomes
(9)
Substitution of equation 8 into equation 9 gives a hydro-
carbon transport equation in water of
(10)
Thomas (1982) solved equation 10 by a finite-differ-
ence method, and Saeed (1991) applied it to vertical
migration. The finite-difference method divides the
region of interest into small blocks. Time is divided into
small steps, which are solved in sequence. The partial dif-
ferential equations are replaced by their finite-difference
equivalents, which results in algebraic equations that are
approximations of the original partial differential equa-
tions. We determined the concentration of the hydrocar-
bon at the center of the blocks by solving the algebraic
equations using the strongly implicit procedure of
Thomas (1982).
Equation 10 was rewritten for each grid point of vol-
ume v within the pore solutions as
(11)
Thomas (1982) transformed the two volume integrals
of equation 11 to surface integrals by using the Gauss
divergence theorem. If the volume of each block is small,
its porosity and density are assumed to be constant, as is
the concentration C of the hydrocarbon. The transforma-
tion to surface integrals gives
(12)
We approximated the dispersive integral in equation
12 for two-dimensional flow by considering only four
faces of the finite difference block:
(13)
To solve the equations, both initial and boundary con-
ditions must be defined. An initial hydrocarbon gas con-
centration is entered as a constant value at the level of the
reservoir, C
0
. The flux is the sum of the dispersive and
advective fluxes. The dispersive term decreases the flux,
and the concentration changes vertically. The computer
program GASINWAT was modified by Saeed (1991) from
one documented by Healy (1990) for modeling of solute
flow in water. Modifications by Saeed allow varying
porosities and permeabilities in the overlying sedimen-
tary column, the compressibility of water, and the solu-
bility change of a hydrocarbon with pressure.
Figure 4 shows the calculated dissolved concentration
of light hydrocarbons dissolved in water ascending at
10
12
m/sec for a period of 10,000 years; other input para-
meters are given in the figure caption. Little dissolved
hydrocarbons reach the surface in this short period of
time. By increasing the permeabilities of the layers and
using much longer times, appreciable light hydrocarbons
are shown to reach the surface (Figure 5).
The exsolution of the dissolved hydrocarbon into the
gaseous phase near the surface is controlled to some
extent by Henrys law, although this is a heterogeneous
process that may result in some degree of gas supersatu-
ration in the aqueous phase. Slow evaporation of ground-
D Cnds D Cnds
t
s s
i
t i
i

1
4
v
C
t
D Cnds v Cnds
s
t
s

( )

C
t
dv D Cdv vCdv
v v
t
v
( )

C
t
D VC
t C
( )

( ) C
t
QC
162 Klusman and Saeed
Figure 3Calculated compaction-driven flow within a
basin cross section. Equipotentials are at intervals of
0.001 MPa (0.01 atm). The flow velocities v
x
and v
z
are rel-
ative to the subsiding medium. (From Bethke, 1985.)
water would increase the concentration observed in the
soil gas, although this cannot be quantitatively predicted.
If the process operated for a long period of time, adsorp-
tion sites in the unsaturated sediment and soil would
become saturated. The free soil gas concentration of
hydrocarbons would reach dynamic equilibrium, but
vary over short time periods due to meteorologic and sea-
sonal parameters (Klusman, 1993). The adsorbed soil gas
concentrations would likely remain more constant than
free soil gas, particularly over the time frame of meteoro-
logic variations. Seasonal variations would likely remain
significant in samples taken in the top few meters
(Klusman, 1993).
The upward migration of connate waters associated
with hydrocarbon reservoirs is supported by heat flow
measurements. Meyer and McGee (1985) measured high-
er temperature gradients over 15 of 22 oil and gas fields
sampled in the Rocky Mountain province. Bodner and
Sharp (1988) found elevated subsurface temperatures
along the Wilcox growth fault in the Gulf Coast. They
proposed upward migration of fluids along the fault,
increasing the temperature gradient. Hanor (1987)
demonstrated convective transport of connate waters
associated with the Iberia salt dome in Louisiana.
The transport of hydrocarbons by water should allow
detection at the surface and not preclude water transport
as a mechanism for vertical migration. The locations of
anomalous free or adsorbed soil gas samples relative to a
subsurface reservoir would be determined largely by
hydrodynamic flow. This mechanism is not sufficiently
rapid, however, to account for the rapid change in the
character of the surface anomaly with initiation of pro-
duction. The data of Hanor (1987) suggest flows of a few
meters per year.
Transport of Hydrocarbons by Buoyancy of
Microbubbles
Transport of hydrocarbons by buoyancy of microbub-
bles occurs when capillary pressure of a microbubble of a
gaseous hydrocarbon exceeds the water displacement
pressure of the largest interconnected pores in a cap rock.
Watts (1987) classified these as membrane seals. Berg (1975)
described membrane seals in stratigraphic traps, and
Schowalter (1979) compared the effectiveness of seals
against the migration of gas compared to penetration by
oil. The threshold displacement pressure required to dis-
place water increases as the permeability of the cap rock
decreases (Katz and Coats, 1968). Another variation in the
cap rock seal is the hydraulic seal (Watts, 1987). This seal
functions until there is some degree of overpressure in the
reservoir, when the seal opens as a fracture. The scale of
fracturing is important in the manifestations of the leak-
age (Watts, 1987). Microfractures are sufficient to allow
seal penetration by gaseous hydrocarbons. Larger frac-
tures and faults may result in upward streaming of two-
phase hydrocarbon and water mixtures (Watts, 1987).
MacElvain (1969) was apparently the first to describe
the buoyancy of microbubbles in the context of surface
exploration. He described rates of vertical migration that
was possibly on the order of several millimeters per sec.
The overlying sedimentary column has some capacity for
adsorption of light hydrocarbons, as indicated by thermal
stripping of well cuttings, but when this capacity is
exceeded, the microbubbles move unimpeded in an
Chapter 12Comparison of Light Hydrocarbon Microseepage Mechanisms 163
Figure 4Calculated concentration of methane, ethane,
and n-butane (in ppm by weight) versus depth after 10,000
years of migration from a reservoir at 1000 m depth. The
reservoir is overlain by a single lithology with a permeabil-
ity of 10
3
md, a diffusion coefficient of 10
10
m
2
/sec, a
porosity of 20%, and a water flux rate of 10
12
m/sec.
(Modified from Saeed, 1991; Klusman, 1993.)
Figure 5Calculated concentration of methane, ethane,
and n-decane (in ppm by weight) versus depth after
500,000 years of migration from a reservoir at 1000 m
depth. The reservoir is overlain by three lithologies:
lithology 1 is 200 m thick and has a permeability of 10
5
md; lithology 2 is 400 m thick with a permeability of 10
3
md; and lithology 3 is 400 m thick with a permeability of
0.1 md. All lithologies have a porosity of 20%, a diffusion
coefficient of 10
10
m
2
/sec, and a water flux rate of 10
9
m/sec. (Modified from Saeed, 1991; Klusman, 1993.)
approximately vertical direction. MacElvain (1969) pro-
posed bubbles of a size that would generate significant
Brownian motion, which would prevent adsorption. This
seems unlikely, and does not have to be prevented if the
adsorptive capacity of the overlying sediments has been
satisfied by earlier microseepage (Klusman, 1993). Differ-
ential adsorption of alkanes by the sedimentary matrix
results in the occasional occurrence of a chromatographic
effect. If the system is in steady-state equilibrium with a
reservoir of constant composition, the adsorptive sites
will not have any additional chromatographic capacity
and additional fractionation will not occur. Also, the sol-
ubility of heavier hydrocarbons in the gas phase decreas-
es with temperature and pressure, resulting in the lighter
hydrocarbons dominating in a soil gas (Price et al., 1983;
Price, 1986).
The basic equations describing hydrocarbon gas and
water flow in porous media are the continuity equations
for each phase. For both gas and water, Darcys law is
proportional to the potential gradient of each phase (Tek
et al., 1966). The velocity of transport for water and gas
can be written as follows (Saeed, 1991; Klusman, 1993):
(14)
and
(15)
where V
w
and V
g
are the velocities of water and gas, K is
the rock permeability, K
w
and K
g
are the relative perme-
abilities of water and gas,
w
and
g
are the viscosities of
water and gas, and
w
and
g
are the water and gas poten-
tials, both defined as P + gh. Gas and water relative per-
meabilities are related to the degree of gas or water satu-
ration. The pressure in the gas phase exceeds that in the
water by the capillary pressure, P
c
, and
(16)
where P
g
and P
w
are the pressures of water and gas, g is
the acceleration due to gravity,
g
and
w
are the densities
of water and gas, and h is the column height. The rela-
tionship between capillary pressure and water saturation,
s, with respect to time is
(17)
This can be combined with equation 16 to give the rela-
tionship between capillary pressure and time:
(18)
The following simultaneous non-linear partial differ-
ential equations for both gas and water potentials as
dependent variables are obtained:
(19)
and
(20)
where Q
g
and Q
w
are gaseous hydrocarbon and water
fluxes and is the water content.
Gas displaces water, so the sum of the fluxes is one,
and migration is only considered in the upward direction
because of buoyancy. Equations 19 and 20 modified by
Crichlow (1977) allow solution by finite-difference meth-
ods. The original computer code written by Tek et al.
(1966) was modified by Saeed (1991) to model hydrocar-
bon gas migration by buoyancy of microbubbles.
Figure 6 shows hydrocarbon gas potential with depth
over short time periods as calculated by the program
GASWATER. The simulated reservoir was at a depth of
1000 m and had a single lithology as overburden, a per-
meability of 0.001 md, and a porosity of 10%. The reser-
voir was overpressured at a total pressure of 3000 psi
(20,700 kPa). There were rapid changes in gas potential
above the reservoir, but not readily discernible at the sur-
face.
Figure 7 shows the hydrocarbon gas potential over
short time periods at three different reservoir pressures.
As in Figure 6, the simulated reservoir was 1000 m deep
and had a single lithology as overburden, a permeability
of 0.001 md, and a porosity of 10%. The modeled reser-
voir pressures were 1500 psi (10,300 kPa), 2000 psi (13,800
kPa), and 3000 psi (20,700 kPa). These pressures are
slightly below hydrostatic pressure, just above hydrostat-
ic pressure, and well above hydrostatic pressure, respec-
tively. Curves A, B, and C on Figure 7 are for a location 10
m below the surface. Curves D, E, and F are for a location
100 m above the reservoir. Again, only small differences
are noted at the near-surface locations relative to the loca-
tion just above the reservoir.
Figure 8 is an expanded view of the upper left corner
of Figure 7, showing only the data for the location 10 m
below the surface. The greater the magnitude of the reser-
voir pressure, the greater the change in gas potential at
the surface in short time intervals. If production were to
occur from the simulated reservoir, rapid changes would
be observed both in the reservoir and at the near-surface
location. This is consistent with observations of enhanced
leakage discussed in the introduction on pressure
changes in demand gas storage reservoirs.
The plot in Figure 9 shows the calculated change in gas
potential pressure 10 m below the surface for different
simulated reservoir pressures, again at a depth of 1000 m.
If the reservoir pressure were abruptly changed from
+

_
,

K
K
Q
s
P
C
w
w
w w
g
w
t t

_
,

K
K
Q
s
P
C
g
g
g g
g
w
t t

P
t
C

( ) g w
t

s
t
s
P
P
t
C
C

P P P gh
c g w g w w g

( )
+
( )

V K
K
g
g
g
g

V K
K
w
w
w
w

164 Klusman and Saeed
2000 psi (13,800 kPa) to 1500 psi (10,300 kPa), a change in
gas potential of 41 kPa would be observed in the near sur-
face in 10 years. Achange in reservoir pressure from 3000
psi (20,700 kPa) to 1500 psi (10,300 kPa) would change the
gas potential by 170 kPa in the same time period. The sim-
ulated change in gas potential declines relatively rapidly
after 10 years for a low-pressure reservoir and after 40
years for a high-pressure reservoir.
Modeling of the buoyancy of microbubbles of gas by
Saeed (1991) supports this mechanism as responsible for
vertical migration. It satisfies our difficult requirement
that migration be close to vertical, so that anomalies
remain sharply defined at the surface. The simulation of
this mechanism also predicts the rapid response in gas
potential and in observed soil gas concentration changes
at the surface.
Araktingi et al. (1982) described the failure of a fault
seal in the Leroy gas storage reservoir in southwestern
Wyoming. The fault seal failure was intermittent, in direct
response to the reservoir pressure changes. Copious leak-
age was noted at the surface a few years after overpres-
suring the reservoir. They described this phenomenon as
acting like a check valve, although a more appropriate
term might be pressure relief valve such as on a water
heater. With overpressuring, the fault (valve) opened,
allowing copious leakage until the pressure dropped
below the capillary entry pressure. Then the fault (valve)
closed again. The transport rate of gas to the surface was
on the order of 1000 ft/year (~300 m/year). In this case,
the system was acting as a hydraulic seal, using Watts
(1987) terminology.
Arp (1992) described pressure-induced leakage from
the Patrick Draw field in southwestern Wyoming.
Produced gas, as well as water, were reinjected into the
field to maintain pressure. Initial gas injection is thought to
have begun about 19601962; there were reports of surface
vegetation die-off by 1980 due to saline water and because
of anaerobic soils as hydrocarbons displaced oxygen. This
translates to a transport rate 250 ft/year (~75 m/year).
Large petroleum production increases began in the
19731975 period. If the die-off that started in 1980 is relat-
ed to the production increase, the transport rate for hydro-
carbons and water exceeds 1000 ft/year (~300 m/year).
We must be careful not to interpret these examples
strictly as buoyancy of microbubbles. The Leroy storage
reservoir described by Araktingi et al. (1982) and the
Patrick Draw oil field leakage described by Arp (1992)
represent atypical flow rates. The leakage from Patrick
Draw was certainly two-phase, as evidenced by observa-
tions of saline water and extreme concentrations of
hydrocarbons in the soil gas.
CONCLUSIONS
Three mechanisms proposed for vertical migration
and microseepage have been evaluated: diffusion, trans-
port by ascending water, and buoyancy of microbubbles.
All three mechanisms can produce surface anomalies.
Chapter 12Comparison of Light Hydrocarbon Microseepage Mechanisms 165
Figure 6Calculated hydrocarbon gas potential versus
depth after 2, 5, 10, and 27 years. A single lithology with a
permeability of 0.001 md and a porosity of 10% overlies
the reservoir at 1000 m depth. Reservoir pressure is 3000
psi (20,700 kPa). (Modified from Saeed, 1991; Klusman,
1993.)
Figure 7Calculated hydrocarbon gas potential versus
time as a function of reservoir gas potential. Asingle
lithology with a permeability of 0.001 md and a porosity of
10% overlies the reservoir at 1000 m depth. Curves A, B,
and C (far left) are 10 m below the surface with reservoir
pressures of 1500 psi (10,300 kPa), 2000 psi (13,800 kPa),
and 3000 psi (20,700 kPa), respectively. Curves D, E, and F
are 100 m above the reservoir with reservoir pressures of
1500 psi (10,300 kPa), 2000 psi (13,800 kPa), and 3000 psi
(20,700 kPa), respectively. (Modified from Saeed, 1991;
Klusman, 1993.)
Diffusion may be the dominant transport mechanism
in the short interval above the water table, but it cannot
be the dominant mechanism through the entire saturated
zone. One major problem is the speed of transport, even
though Leythaeuser et al. (1982), Krooss et al. (1992a, b),
and Nelson and Simmons (1992, 1995) proposed that gas
reservoirs are somewhat ephemeral during geologic time.
Other observations not satisfied by a diffusion mecha-
nism are (1) close correspondence of a projection of the
subsurface reservoir with the anomaly on the surface, (2)
sharp lateral variations that would be blurred if diffusion
were the principal mechanism (Rice, 1986), and most seri-
ously, (3) the disappearance of anomalies after produc-
tion starts (Horvitz, 1969). The role of diffusion in prima-
ry migration remains viable (Thomas and Clouse,
1990a,b,c).
The mechanism of vertical transport by dissolution in
water suffers many of the same problems as transport by
diffusion. Significant lateral offset of surface anomalies
would be much more common, and gas anomalies direct-
ly above the reservoir would be rare. Dispersion, result-
ing in blurred anomalies, would be the norm, and halo
anomalies would be rare. The rapid disappearance of a
surface anomaly with initiation of production also would
not occur with the water transport mechanism. The role
of water transport in secondary migration is likely a
major factor (Tth, 1988).
Ascending buoyant microbubbles of gaseous hydro-
carbons is the third mechanism that was discussed.
Modeling by Saeed (1991) supports this as the dominant
mechanism for vertical migration and as responsible for
surface anomalies. This was also the conclusion of Price
(1986). This favored mechanism can explain near-vertical
migration in the absence of faulting and normal slow
rates of lateral water flow in a basin. It also explains
anomalies that are directly above the surface projection of
reservoirs. Indirect effects such as secondary cementation
of part of the sedimentary column result in halo anom-
alies due to diversion of microseepage around the
cemented chimney produced by oxidation-reduction
processes (Klusman, 1993). Most importantly, the com-
puter simulations of Saeed (1991) predict rapid changes
in surface anomalies once production from the reservoir
starts.
AcknowledgmentsSupport was provided to M. A. S. by the
U.S. Agency for International Development during part of his
tenure as a student at the Colorado School of Mines. The man-
uscript was improved by the reviews of M. A. Abrams,
D. Schumacher, and particularly W. A. Young.
REFERENCES CITED
Araktingi, R. E., M. E. Benefield, Z. Bessenyei, K. H. Coats,
and M. R. Tek, 1982, Leroy Storage, Uinta County,
Wyoming: a case study of attempted control of gas migra-
tion: 57th Annual Society of Petroleum Engineers of
AIME, Fall Technical Conference, SPE11180, 11 p.
Arp, G. K., 1992, An integrated interpretation for the origin of
the Patrick Draw oil field sage anomaly: AAPG Bulletin,
v. 76, p. 301306.
Bear, J., 1979, Hydraulics of groundwater: New York,
McGraw-Hill, 567 p.
Berg, R. R., 1975, Capillary pressures in stratigraphic traps:
AAPG Bulletin, v. 59, 939956.
166 Klusman and Saeed
Figure 8An expanded view of the upper left corner of
Figure 7 showing only the data for the location 10 m
below the surface. See Figure 7 for parameters. Asignifi-
cant change in gas potential occurs in the near-surface
with change in reservoir pressure over a short period of
time. (Modified from Saeed, 1991; Klusman, 1993.)
Figure 9Calculated change in potential pressure 10 m
below the surface versus time at different reservoir pres-
sures. The significant change in potential pressure with
time results in rapid changes in soil gas anomalies with
production. (Modified from Saeed, 1991; Klusman, 1993.)
Bethke, C. M., 1985, Anumerical model of compaction-driven
groundwater flow and heat transfer and its application to
the paleo-hydrology of intracratonic sedimentary basins:
Journal Geophysical Research, v. 90, p. 68176828.
Bodner, D. P., and J. M. Sharp, Jr., 1988, Temperature varia-
tions in south Texas subsurface: AAPG Bulletin, v. 72,
p. 2132.
Buckley, S. E., C. R. Hocott, and M. S. Taggart, Jr., 1958,
Distribution of dissolved hydrocarbons in subsurface
waters, in L. G. Weeks, ed., Habitat of oil: Tulsa,
Oklahoma, AAPG, p. 850882.
Coleman, D. D., W. F. Meents, C.-L. Liu, and R. A. Keogh,
1977, Isotopic identification of leakage gas from under-
ground storage reservoirsa progress report: Illinois State
Geological Survey, Report 111, 10 p.
Crichlow, H. B., 1977, Modern reservoir engineeringa sim-
ulation approach: Englewood Cliffs, New Jersey, Prentice-
Hall, 354 p.
Devitt, D. A., R. B. Evans, W. A. Jury, T. H. Starks, B. Eklund,
A. Gnolson, and J. J. van Ee, 1987, Soil gas sensing for
detection and mapping of volatile organics: Dublin, Ohio,
National Water Well Association, 270 p.
Hanor, J. S., 1987, Kilometre-scale thermohaline overturn of
pore water in the Louisiana Gulf Coast: Nature, v. 327,
p. 501503.
Healy, R. W., 1990, Simulation of solute transport in variably
saturated porous media with supplemental information
on modification to the U.S. Geological Survey computer
program VS2D: USGS Water Resources Investigation
Report 90-4025, 125 p.
Horvitz, L., 1969, Hydrocarbon geochemical prospecting after
thirty years, in W. B. Heroy, ed., Unconventional methods
in exploration for petroleum and natural gas: Dallas,
Texas, Southern Methodist University Press, p. 205218.
Jakel, M. E., and R. W. Klusman, 1995, Methane fluxes to the
atmosphere due to natural microseepage from sedimenta-
ry basins (abs.): American Geophysical Union, EOS, v. 76,
no. 46, p. F126.
Jones, P. H., 1984, Deep water discharge: a mechanism for the
vertical migration of oil and gas, in M. J. Davidson and B.
M. Gottlieb, eds., Unconventional methods in exploration
for petroleum and natural gas, III: Dallas, Texas, Southern
Methodist University Press, p. 254271.
Katz, D. L., and K. H. Coats, 1968, Underground storage of
fluids: Ann Arbor, Michigan, Ulrichs Books, Inc., 575 p.
Klusman, R. W., 1993, Soil gas and related methods for natur-
al resource exploration: Chichester, U.K., John Wiley &
Sons, 483 p.
Krooss, B. M., D. Leythaeuser, and R. G. Schaefer, 1992a, The
quantification of diffusive hydrocarbon losses through cap
rocks of natural gas reservoirsa reevaluation: AAPG
Bulletin, v. 76, p. 403406.
Krooss, B. M., D. Leythaeuser, and R. G. Schaefer, 1992b, The
quantification of diffusive hydrocarbon losses through cap
rocks of natural gas reservoirsa reevaluation: Reply:
AAPG Bulletin, v. 76, p. 18421846.
Leythaeuser, D., R. G. Schaefer, and A. Yukler, 1980, Diffusion
of light hydrocarbons through near-surface rocks: Nature,
v. 284, p. 522525.
Leythaeuser, D., R. G. Schaefer, and A. Yukler, 1982, Role of
diffusion in primary migration of hydrocarbons: AAPG
Bulletin, v. 66, p. 408429.
McAuliffe, C. D., 1979, Oil and gas migrationchemical and
physical constraints: AAPG Bulletin, v. 63, p. 761781.
MacElvain, R., 1969, Mechanics of gaseous ascension through
a sedimentary column, in W. B. Heroy, ed.,
Unconventional methods in exploration for petroleum
and natural gas: Dallas, Texas, Southern Methodist
University Press, p. 1528.
Magara, K., 1978, Compaction and fluid migration; practical
petroleum geology: Amsterdam, Elsevier, 319 p.
Meyer, H. J., and H. W. McGee, 1985, Oil and gas fields
accompanied by geothermal anomalies in Rocky
Mountain region: AAPG Bulletin, v. 69, p. 933945.
Neglia, S., 1979, Migration of fluids in sedimentary basins:
AAPG Bulletin, v. 63, p. 573597.
Nelson, J. S., and E. C. Simmons, 1992, The quantification of
diffusive hydrocarbon losses through cap rocks of natural
gas reservoirsa reevaluation: Discussion: AAPG
Bulletin, v. 76, p. 18391841.
Nelson, J. S., and E. C. Simmons, 1995, Diffusion of methane
and ethane through the reservoir cap rock, and its impli-
cations for the timing and duration of catagenesis: AAPG
Bulletin, v. 79, p. 10641074.
Price, L. C., 1976, Aqueous solubility of petroleum as applied
to its origin and primary migration: AAPG Bulletin, v. 60,
p. 213244.
Price, L. C., 1986, Acritical overview and proposed working
model of surface geochemical exploration, in M. J.
Davidson, ed., Unconventional methods in exploration for
petroleum and natural gas, IV: Dallas, Texas, Southern
Methodist University Press, p. 245309.
Price, L. C., L. M. Wenger, T. Ging, and C. W. Blount, 1983,
Solubility of crude oil in methane as a function of pressure
and temperature: Organic Geochemistry, v. 4, p. 201221.
Rice, G. K., 1986, Near-surface hydrocarbon gas measurement
of vertical migration, in M. J. Davidson, ed.,
Unconventional methods in exploration for petroleum
and natural gas, IV: Dallas, Texas, Southern Methodist
University Press, p. 183220.
Saeed, M. A., 1991, Light hydrocarbon microseepage mecha-
nisms: theoretical considerations: Ph.D. dissertation,
Colorado School of Mines, Golden, Colorado, 128 p.
Schowalter, T. T., 1979, Mechanics of secondary hydrocarbon
migration and entrapment: AAPG Bulletin, v. 63, p.
723760.
Spencer, C. W., 1987, Hydrocarbon generation as a mecha-
nism for overpressuring in Rocky Mountain region:
AAPG Bulletin, v. 71, p. 368388.
Stegena, L., 1961, On the principles of geochemical oil
prospecting: Geophysics, v. 26, p. 447451.
Tek, M., J. O. Wilkes, and D. Katz, 1966, New concepts in
underground storage of natural gas: New York, American
Gas Association, 342 p.
Thomas, C. W., 1982, Principles of hydrocarbon reservoir
simulation: Boston, IHRDC, 207 p.
Thomas, M. M., and J. A. Clouse, 1990a, Primary migration
by diffusion through kerogen: I. model experiments with
organic-coated rocks: Geochimica et Cosmochimica Acta,
v. 54, p. 27752779.
Thomas, M. M., and J. A. Clouse, 1990b, Primary migration
by diffusion through kerogen: II. hydrocarbon diffusivities
in kerogen: Geochimica et Cosmochimica Acta, v. 54,
p. 27812792.
Thomas, M. M., and J. A. Clouse, 1990c, Primary migration
by diffusion through kerogen: III. calculation of geologic
fluxes: Geochimica et Cosmochimica Acta, v. 54,
p. 27932797.
Chapter 12Comparison of Light Hydrocarbon Microseepage Mechanisms 167
Tth, J., 1988, Ground water and hydrocarbon migration, in
W. Back, J. S. Rosenshein, and P. R. Seaber, eds., The geolo-
gy of North Americahydrogeology, GSA, v. O-2,
p. 485502.
Warneck, P., 1988, Chemistry of the natural atmosphere: San
Diego, Academic Press, 757 p.
Watts, N. L., 1987, Theoretical aspects of cap-rock and fault
seals for single- and two-phase hydrocarbon columns:
Marine and Petroleum Geology, v. 4, p. 274307.
Whelan, J. K., J. M. Hunt, J. Jasper, and A. Huc, 1984,
Migration of C
1
C
8
hydrocarbons in marine sediments:
Organic Geochemistry, v. 6, p. 683694.
168 Klusman and Saeed