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1029/2009WR008712, 2010
Citation: OCarroll, D. M., K. G. Mumford, L. M. Abriola, and J. I. Gerhard (2010), Influence of wettability variations on
dynamic effects in capillary pressure, Water Resour. Res., 46, W08505, doi:10.1029/2009WR008712.
1. Introduction
[2] Continuumbased multiphase flow simulators used to
predict the migration of nonaqueous phase liquids (NAPLs)
in porous media commonly incorporate a constitutive expression relating capillary pressure and saturation (PcS). These
relationships have been shown to be a function of the rate of
change in saturation [e.g., Topp et al., 1967; Smiles et al.,
1971; Vachaud et al., 1972; Stauffer, 1978; Hassanizadeh
et al., 2002; Berentsen et al., 2006; Sakaki et al., 2010],
which creates a nonuniqueness in PcS relationships that is
not related to hysteresis (flow reversals). This dependence on
the flow conditions has been attributed to dynamic effects in
capillary pressure [Kalaydjian, 1987; Hassanizadeh and
Gray, 1990]. A number of expressions that are similar in
mathematical form have been proposed to model the nonuniqueness associated with dynamic effects, including
dynamic capillary pressure [Stauffer, 1978; Barenblatt and
1
Department of Civil and Environmental Engineering, University of
Western Ontario, London, Ontario, Canada.
2
Department of Civil Engineering, Queens University, Kingston,
Ontario, Canada.
3
School of Engineering, Tufts University, Medford, Massachusetts,
USA.
@sw
;
@t
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dynamic effects and wettability based on interface movement in a single capillary tube.
;
DP
r
r2
dt
1 l1 2 l2
L
212 cos 8L dl
2
;
r
r
dt
212 cos d 8L dl
dl
2
; d f
;
r
r
dt
dt
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3m
LM
9Ca ln
Lm
[Blake, 2006], where z is a coefficient of contact line friction. Blake and Haynes [1969] successfully applied the
molecularkinetic approach to describe the dynamic contact
angles for a benzenewater interface in a glass capillary
treated with trimethylchlorosilane. The value of z is given
by
exp
"
#
Dgs* 2
kB T
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212
dl
8L dl
2
cos
12 dt
r
dt
r
10
dt
2
8L 1
212 cos
DP
2
:
r
r
r
11
12
tube
2
8L
2 :
r
r
13
W08505
Water
3
Density (kg/m )
Viscosity (Ns/m2)
999
1.12 103
PCE
1630
9.0 104
14
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Treatment
Receding
Contact
Angle on
Glass Slideb
66.4 (4.4)
Octadecyltrichlorosilane (OTS)
137.6 (18.0)
Operative Contact
Angle During
Drainage Based
on PcS Scalingc
64.4 (1.7)d,
82.3 (1.4)e
83.4 (0.7)
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41.8
44.9
47.3
49.2
52.1
55.1
61.9
67.9
75.9
2.6
3.0
2.5
1.9
3.0
3.0
6.8
6.0
8.0
1.00
0.98
0.96
0.61
0.49
0.21
0.14
0.02
0.00
46.8
48.4
53.4
59.0
3.9
1.6
4.9
5.6
1.00
0.98
0.03
0.00
34.8
35.7
36.9
40.0
41.8
44.7
47.5
52.0
56.8
65.4
1.4
1.0
1.2
3.0
1.8
2.9
2.8
4.6
4.8
8.6
1.00
0.95
0.87
0.80
0.34
0.24
0.10
0.04
0.01
0.00
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MSORDSA
MSORDSB
MSOOTS
1.08 1011
3.48 1015
7.12 1014
0.311
1.23 1011
6.48 1015
2.77 1014
0.319
1.11 1011
6.62 1015
4.70 1014
0.301
6.35 102
7.17
0.24
1.50
1.72 101
1.38 101
8.0
0.0
2.08
3.56 101
2.25 101
4.42
0.14
1.05
1.69 101
6.69 102
6.61
0.24
3.43 107
0.57
62%
1.51 101
1.50 101
8.0
0.0
2.76 106
1.20
42%
3.34 101
2.28 101
4.74
0.17
3.74 106
0.70
33%
1.60 101
w g ;
Sw
@z
@Pw @t
@Pc @t
@z
15
@
n @ Pcs Pw
@Sn @Pcs
n s
@Pn
@P
@t
@t
c
s
@ Pc Pw
@
@
@Sw @Pcs
n
g
;
n
@z
@z
@Pcs @t
@z
ASe A;
16
1=n
1 1=m
Se 1
;
17
18
h
im
krn 1 Se 2 1 Se1=m ;
19
20
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Figure 3. Comparison of equilibrium drainage measurements (symbols) and van Genuchten curves
(lines) derived from parameter optimization in the simulation of multistep outflow data, assuming no
dynamic effects. Parameters derived from MSO data simulations incorporating dynamic effects, as
described by equations 1 and 20, produced similar van Genuchten curves, which are not shown for clarity.
equilibrium measurements. Sand and membrane intrinsic
permeability, measured independently according to the
method of OCarroll et al. [2005b], were inputs for the model
and are listed in Table 4. It is important to note that the t
values obtained in the study, calculated using equation 20 and
fitted A values, represent smallscale (i.e., local) damping
coefficients [OCarroll et al., 2005b; Berentsen et al., 2006].
This is in contrast to other studies that have reported macroscopic t values based on averaging pressures and saturations over length scales of 3 to 100 cm [Manthey et al., 2005;
Das et al., 2007; Mirzaei and Das, 2007].
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Q Qi
;
Qf Qi
21
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Figure 5. Selected, scaled outflow steps from the multistep outflow experiments in RDS and OTS
treated sand, compared to outflow steps from previously conducted multistep outflow experiments in
waterwet sand [OCarroll et al., 2005b].
Figure 4a, and the best fit values of the parameters are listed
in Table 4 along with the RMSEQ values. The simulated
outflow curves for each of the experiments fails to capture
the approach rate to zero outflow and the steady cumulative
outflow value. Simulated curves tend to exhibit a more rapid
approach to steady cumulative outflow and achieve a lower
cumulative outflow plateau as the system reaches equilibrium. Similar differences have been observed for simulations of MSO outflow data during the drainage of waterwet
sands [Chen et al., 1999; Schultz et al., 1999; Hwang and
Powers, 2003; OCarroll et al., 2005b]. It has been previously reported that this slower approach to zero outflow in a
PCE/water/quartz sand system could not be matched by a
simulator that neglects dynamic effects [OCarroll et al.,
2005b]. The lower steady cumulative value obtained in the
simulations is a consequence of the rootmeansquare error
minimization procedure, where minimization of the objective function causes the model to undershoot the plateau
while overshooting its rate of approach. The differences
between the observed and simulated values is more apparent
in data from MSORDSA than from MSORDSB or MSO
OTS, but the differences are generally less than those reported
for MSO experiments in waterwet sands [OCarroll et al.,
2005b].
[33] Fit values of the PcS function parameters using t = 0
were used to generate PcS curves using equation 17 for each
of the three sands and are compared to data from the equilibrium drainage experiments in Figure 3. Also included, for
comparison, is the PcS curve for the waterwet sand generated using parameters fit using inverse modeling to data from
MSOWWA [OCarroll et al., 2005b]. The rootmean
square errors for the PcS curves were calculated based on the
difference between the measured and VG modelgenerated
values of Se (RMSES) and are listed in Table 4. The RMSES
was based on differences in Se rather than Pc to reduce the
importance of data at high and low effective water satura-
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References
Abriola, L. M., A. H. Demond, D. M. OCarroll, H. L. Hsu, T. J. Phelan,
C. A. Polityka, and J. L. Ryder (2005), Compositional effects on interfacial properties in contaminated systems: Implications for organic liquid
migration and recovery, in Subsurface Contamination Remediation,
edited by E. Berkey and T. Zachry, pp. 160182, Am. Chem. Soc.,
Washington, DC.
Adamson, A. W. (1982), Physical Chemistry of Surfaces, 4th ed., John Wiley,
New York, NY.
Anderson, R., G. Larson, and C. Smith (1991), Silicon Compounds: Register
and Review, 5th ed., Huls America, Piscataway, NJ.
Anderson, W. G. (1986), Wettability literature survey. 1. Rockoilbrine
interactions and the effects of core handling on wettability, J. Pet.
Technol., 38(11), 11251144.
Anderson, W. G. (1987a), Wettability literature survey. 4. Effects of wettability on capillarypressure, J. Pet. Technol., 39(10), 12831300.
Anderson, W. G. (1987b), Wettability literature survey. 5. The effects of
wettability on relative permeability, J. Pet. Technol., 39(11), 14531468.
Barenblatt, G. I., and A. A. Gilman (1987), Nonequilibrium counterflow
capillary impregnation, J. Eng. Phys., 52, 335339.
Barranco, F. T., and H. E. Dawson (1999), Influence of aqueous pH on
the interfacial properties of coal tar, Environ. Sci. Technol., 33(10),
15981603.
Berentsen, C. W. J., S. M. Hassanizadeh, A. D. Bezuijen, and O. Oung
(2006), Modeling of twophase flow in porous media including nonequilbrium capillary pressure effects, in XVI International Conference
on Computational Methods in Water Resources, Copenhagen, Denmark.
Blake, T. D. (2006), The physics of moving wetting lines, J. Colloid Interface Sci., 299(1), 113.
Blake, T. D., and J. M. Haynes (1969), Kinetics of liquid/liquid displacement, J. Colloid Interface Sci., 30(3), 421423.
Blake, T. D., and J. De Coninck (2002), The influence of solidliquid interactions on dynamic wetting, Adv. Colloid Interface Sci., 96(13), 2136.
W08505
12 of 13
W08505
Hiemenz, P. C., and R. Rajagopalan (1997), Principles of Colloid and Surface Chemistry, 3rd ed., xix, 650 pp., Marcel Dekker, New York.
Hoffman, R. L. (1975), Study of advancing interface.1. Interface shape in
liquidgas systems, J. Colloid Interface Sci., 50(2), 228241.
Hsu, H. L., and A. H. Demond (2007), Influence of organic acid and
organic base interactions on interfacial properties in NAPLwater systems, Environ. Sci. Technol., 41(3), 897902.
Hwang, S. I., and S. E. Powers (2003), Estimating unique soil hydraulic
parameters for sandy media from multistep outflow experiments, Adv.
Water Resour., 26(4), 445456.
Hwang, S. I., K. P. Lee, D. S. Lee, and S. E. Powers (2006), Effects of fractional wettability on capillary pressuresaturationrelative permeability
relations of twofluid systems, Adv. Water Resour., 29(2), 212226.
Juanes, R. (2008), Nonequilibrium effects in models of threephase flow in
porous media, Adv. Water Resour., 31(4), 661673.
Kalaydjian, F. (1987), A macroscopic description of multiphase flow in
porousmedia involving spacetime evolution of fluidfluid interface,
Transp. Porous Media, 2(6), 537552.
Kool, J. B., J. C. Parker, and M. T. van Genuchten (1985), Determining soil
hydraulicproperties from onestep outflow experiments by parameter
estimation. 1. Theory and numericalstudies, Soil Sci. Soc. Am. J.,
49(6), 13481354.
Lee, S. L., and H. D. Lee (2007), Evolution of liquid meniscus shape in a
capillary tube, J. Fluids Eng., 129(8), 957965.
Leverett, M. C. (1941), Capillary behavior in porous solids, Trans. AIME,
142, 152170.
Liu, Y. P., J. W. Hopmans, M. E. Grismer, and J. Y. Chen (1998), Direct
estimation of airoil and oilwater capillary pressure and permeability
relations from multistep outflow experiments, J. Contam. Hydrol.,
32(34), 223245.
Lord, D. L., K. F. Hayes, A. H. Demond, and A. Salehzadeh (1997), Influence of organic acid solution chemistry on subsurface transport properties. 1. Surface and interfacial tension, Environ. Sci. Technol., 31(7),
20452051.
Lord, D. L., A. H. Demond, and K. F. Hayes (2000), Effects of organic
base chemistry on interfacial tension, wettability, and capillary pressure
in multiphase subsurface waste systems, Transp. Porous Media, 38(12),
7992.
Lord, D. L., A. H. Demond, and K. F. Hayes (2005), Comparison of capillary
pressure relationships of organic liquidwater systems containing an
organic acid or base, J. Contam. Hydrol., 77(3), 195208.
Lunati, I., and D. Or (2009), Gravitydriven slug motion in capillary tubes,
Phys. Fluids, 21(5), 9.
Manthey, S., S. M. Hassanizadeh, O. Oung, and R. Helmig (2004),
Dynamic capillary pressure effects in twophase flow through heterogeneous porous media, in XV International Conference on Computational
Methods in Water Resources, Chapel Hill, NC.
Manthey, S., S. M. Hassanizadeh, and R. Helmig (2005), Macroscale
dynamic effects in homogeneous and heterogeneous porous media,
Transp. Porous Media, 58(12), 121145.
Manthey, S., S. M. Hassanizadeh, R. Helmig, and R. Hilfer (2008), Dimensional analysis of twophase flow including a ratedependent capillary
pressuresaturation relationship, Adv. Water Resour., 31(9), 11371150.
Martic, G., J. De Coninck, and T. D. Blake (2003), Influence of the dynamic
contact angle on the characterization of porous media, J. Colloid Interface
Sci., 263(1), 213216.
Mirzaei, M., and D. B. Das (2007), Dynamic effects in capillary pressure
saturations relationships for twophase flow in 3D porous media: Implications of microheterogeneities, Chem. Eng. Sci., 62(7), 19271947.
Morrow, N. R. (1976), Capillarypressure correlations for uniformly wetted
porousmedia, J. Can. Pet. Technol., 15(4), 4969.
Munson, B. R., D. F. Young, and T. H. Okiishi (1990), Fundamentals of
Fluid Mechanics, John Wiley, Toronto.
OCarroll, D. M., S. A. Bradford, and L. M. Abriola (2004), Infiltration
of PCE in a system containing spatial wettability variations, J. Contam.
Hydrol., 73(14), 3963.
OCarroll, D. M., L. M. Abriola, C. A. Polityka, S. A. Bradford, and A. H.
Demond (2005a), Prediction of twophase capillary pressuresaturation
relationships in fractional wettability systems, J. Contam. Hydrol.,
77(4), 247270.
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