WATER RESOURCES RESEARCH, VOL. 46, W08505, doi:10.

1029/2009WR008712, 2010

Influence of wettability variations on dynamic effects

in capillary pressure
Denis M. OCarroll,1 Kevin G. Mumford,2 Linda M. Abriola,3 and Jason I. Gerhard1
Received 29 September 2009; revised 23 February 2010; accepted 16 March 2010; published 3 August 2010.

Traditional continuumbased multiphase simulators incorporate a capillary pressure

saturation relationship that assumes instantaneous attainment of equilibrium following a
disturbance. This assumption may not be appropriate for systems where the capillary
pressure is a function of the rate of change of saturation, a phenomenon referred to as
dynamic capillary pressure. Previous studies have investigated the impact of soil and fluid
properties on dynamic effects in capillary pressure; however, the impact of wettability on
this phenomenon has not been investigated to date. In this study, twophase multistep
outflow (MSO) experiments conducted in chemically treated sands with different
equilibrium contact angles were used to investigate the influence of wettability variations
on dynamic effects in capillary pressure during displacement of water by tetrachloroethene
(PCE). Data from the MSO experiments were modeled with a multiphase flow
simulator that includes dynamic effects and were also analyzed through comparisons with
theoretical model predictions for interface movement in a single capillary tube. Results
showed that a faster approach to equilibrium, characterized by smaller fitted damping
coefficients, occurred in sands with larger equilibrium contact angles. Damping
coefficients for sands with an operational contact angle greater than 80 were found to be
an order of magnitude smaller than those with an operational contact angle less than 65.
These results suggest that it may be possible to neglect dynamic effects in capillary
pressure in systems that approach intermediatewet conditions but that these effects will be
increasingly important in more waterwet systems.
[1]

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.

Copyright 2010 by the American Geophysical Union.

00431397/10/2009WR008712

Gilman, 1987; Kalaydjian, 1987; Hassanizadeh and Gray,

1990]. These expressions incorporate a finite relaxation
time required for a system to return to an equilibrium state
following a disturbance. The relationship employed in this
study is expressed as [Hassanizadeh and Gray, 1993]:
Pcd Pcs 

@sw
;
@t

where Pdc is the dynamic capillary pressure, Pcs is the static

capillary pressure, Sw is the water saturation, t is time, and t
is a material coefficient, often referred to as the damping
coefficient [Hassanizadeh and Gray, 1993]. In this study the
static capillary pressure (Psc) is defined as the difference
between the nonaqueous and aqueous phase pressures (Pn
Pw) when there is no change in fluid saturation. Dynamic
capillary pressure (Pdc ) is the difference between the nonaqueous and aqueous phase pressures measured at any time.
The static and dynamic capillary pressures are only equivalent at equilibrium (i.e., when Sw/t = 0). Static capillary
pressure, however, can provide a reasonable approximation
of dynamic capillary pressure for systems that reestablish
equilibrium quickly (i.e., t 0). The assumption of t = 0,
and an instantaneous return to equilibrium, is implicit in
common multiphase flow simulators that employ constitutive relationships based on equilibrium capillary pressure
measurements. This assumption may be inappropriate for

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systems where high rates of saturation change are expected,

such as for water infiltration into dry soil [Hassanizadeh
et al., 2002], a rapid release of dense nonaqueous phase
liquid into a water saturated soil, or CO2 sequestration in
deep subsurface systems.
[3] Dynamic effects in capillary pressure have been
investigated in multiple laboratory [e.g., Stauffer, 1978;
Hassanizadeh et al., 2002; Manthey et al., 2004; OCarroll
et al., 2005b; Berentsen et al., 2006; Bottero et al., 2006;
Sakaki et al., 2010] and modeling [e.g., Dahle et al., 2005;
Manthey et al., 2005; Das et al., 2007; Mirzaei and Das,
2007; Juanes, 2008] studies; however, the underlying
mechanisms and controlling parameters remain unclear.
These investigations suggest that the magnitude of the
dynamic effects can be related to fluid properties (viscosity,
density, and interfacial tension), porous medium properties
(intrinsic permeability, porosity, and poresize distribution),
water saturation, and the size of the system under consideration. Some of these studies have proposed functional
relationships for the damping coefficient, based on experimental [Stauffer, 1978] or modeling [Das et al., 2007] work.
Many of the modeling investigations have considered
macroscopic contributions to dynamic effects, including
viscous fingering [Das et al., 2007], macroscopic heterogeneities [Manthey et al., 2005], and boundary pressures
[Manthey et al., 2005]. Other studies, however, have explored
the contributions of smallerscale phenomena, including fine
scale heterogeneities [Mirzaei and Das, 2007], forces acting
at liquidliquid and liquidsolid interfaces [Hassanizadeh
and Gray, 1993], and dynamic contact angles [Friedman,
1999; Wildenschild et al., 2001; Hassanizadeh et al., 2002;
Manthey et al., 2008]. To date, however, the impact of
wettability variations on dynamic effects in capillary pressure has not been explored. While the theory presented by
Hassanizadeh and Gray [1993] implicitly incorporates
wettability by including forces acting at liquidliquid and
liquidsolid interfaces, these investigators did not explicitly
examine the influence of wettability.
[4] Wettability, the tendency of one fluid to spread on or
adhere to a solid surface in the presence of another immiscible fluid [Craig, 1971], is typically represented by the
contact angle , the angle made by a fluidfluid interface in
contact with a solid surface [Hiemenz and Rajagopalan,
1997]. In a NAPLwatersolid system, the solid surface is
referred to as strongly waterwet for  approaching 0 and
strongly NAPLwet for  approaching 180. Solid surfaces
in systems where 60 <  < 130 are typically referred to as
intermediate wet [Morrow, 1976]. Contact angles here refer
to equilibrium contact angles measured through the water
phase. Although it is often assumed that  = 0 in many
porous media systems, where silica is the dominant material
[Anderson, 1986], this assumption may be inappropriate for
materials that do not exhibit strongly waterwet behavior
such as calcite, dolomite, coal, and talc [e.g., Anderson, 1986;
Gooddy et al., 2002], materials coated with natural organic
material [e.g., Abriola et al., 2005; Ryder and Demond,
2008], or surfaces that have been exposed to surfactants or
NAPLs [e.g., Treiber et al., 1972; Barranco and Dawson,
1999; Lord et al., 2000; Harrold et al., 2001; Dwarakanath
et al., 2002; Lord et al., 2005; Hsu and Demond, 2007;
Ryder and Demond, 2008]. Laboratory experiments and
theoretical studies have shown PcS relationships to be a

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function of wettability; lower entry pressures and lower

capillary pressures have been observed at intermediate
saturations during drainage and imbibition for both uniformly
and fractionally wet media that are characterized by larger
contact angles [e.g., Morrow, 1976; Anderson, 1987a;
Bradford and Leij, 1995; Bradford et al., 1997; Ustohal et al.,
1998; OCarroll et al., 2005a; Hwang et al., 2006; Gladkikh
and Bryant, 2007]. These studies, however, have typically
quantified the PcS relationship under equilibrium conditions.
[5] Under nonequilibrium (i.e., moving interface) conditions, the contact between the fluids and the solid can be
characterized by a dynamic contact angle d, which is not
necessarily equal to the equilibrium contact angle [e.g.,
Weisbrod et al., 2009]. The dynamic contact angle is associated with the dependence of the contact angle on the
velocity of the contact line [Hoffman, 1975; Dussan, 1979;
de Gennes, 1985], the line that defines the intersection of the
two fluid phases and the solid. This concept differs from
what is commonly referred to as contact angle hysteresis, the
dependence of the contact angle on the direction of the
contact line movement. The dynamic contact angle has been
shown to decrease with increasing velocity during drainage
and increase with increasing velocity during imbibition
[e.g., Dussan, 1979]. The fundamental disagreement between
conventional hydrodynamic theory, which assumes a noslip
condition at the fluidsolid boundary, and the existence of a
moving contact line has inspired substantial research relating to the dynamics of wetting processes, and to dynamic
contact angles in particular (see recent reviews by Blake
[2006] and Ralston et al. [2008]). The dynamic contact
angle has been related to the contact line velocity and the
static (i.e., equilibrium) contact angle through various functional relationships [e.g., Blake and Haynes, 1969; Hoffman,
1975; Voinov, 1976; Cox, 1986; Zhou and Sheng, 1990;
BrochardWyart and de Gennes, 1992]. The approaches
used to generate these relationships can be generally divided
into two categories: hydrodynamic and molecular kinetic.
Hydrodynamic approaches emphasize energy dissipation due
to viscous effects in a wedge of liquid near the contact line,
and molecularkinetic approaches emphasize a friction force
due to molecularscale adsorption of the advancing fluid and
desorption of the receding fluid at the contact line [Brochard
Wyart and de Gennes, 1992; Blake, 2006; Ralston et al.,
2008].
[6] Friedman [1999] hypothesized that dynamic contact
angles could account for dynamic effects in capillary pressure. That work suggested that decreased contact angles
produced during dynamic drainage would yield higher water
saturations, at a given capillary pressure, when compared to
those produced during equilibrium drainage. Friedman
[1999] suggested that the dynamic effects produced by
dynamic contact angles were likely to be more significant
for NAPLgas systems than waterair systems because of
the lower interfacial tension. The work of Wildenschild et al.
[2001] and Hassanizadeh et al. [2002] supports dynamic
contact angles as a plausible mechanism contributing to
dynamic effects in capillary pressure but suggests that it is
likely to be more significant in NAPLwater systems than in
watergas systems, where equilibrium contact angles are
expected to be larger. In a recent theoretical study by Blake
and De Coninck [2004], the combined effect of wettability
and dynamic contact angle on contact line displacement was

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dynamic effects and wettability based on interface movement in a single capillary tube.

2. Conceptual Model Based on a Single Capillary

Tube Model
Figure 1. Schematic representation of a capillary tube containing a wetting fluid 1 and a nonwetting fluid 2, where the
dotted line represents the fluidfluid interface at equilibrium
and the solid line represents the fluidfluid interface in
motion during drainage.

investigated. Using a molecularkinetic approach, they

showed that the contact line will move more slowly during
drainage or imbibition in systems with a smaller equilibrium
contact angle, all other conditions being the same. On the
basis of these results, it is hypothesized that the wettability
of porous media systems will influence dynamic effects in
capillary pressure.
[7] Multistep outflow (MSO) experiments have been
proposed as a rapid method to obtain porous media constitutive relationships. In a MSO experiment, a packed column
is subjected to successive increases in pressure at the column
inlet and the cumulative outflow is measured. A numerical
solution of Richards equation for airwater systems, or
multiphase flow equations for any twofluid system, is then
used to match observed outflow response. This approach has
been used to rapidly estimate PcS and krS constitutive
relationship parameters in airwater and NAPLwater systems
[Kool et al., 1985; Parker et al., 1985; Eching and Hopmans,
1993; Eching et al., 1994; van Dam et al., 1994; Liu et al.,
1998; Chen et al., 1999; Hwang and Powers, 2003]. The
estimation of these parameters is based on the best fit to
cumulative outflow data. The approach to steady state, however, is frequently modeled to be more rapid than observed
[e.g., Chen et al., 1999; Schultz et al., 1999; Hwang and
Powers, 2003]. Recently, MSO experiments have also been
used to estimate the damping coefficient related to dynamic
effects in capillary pressure [OCarroll et al., 2005b]. In that
study, incorporation of equation 1 into the governing differential equations resulted in a better fit to observed outflow,
particularly for the nonequilibrium portion of the outflow
curve, than alternative model fits obtained assuming validity
of equilibrium capillary pressure and relative permeability
relations (t = 0). Equilibrium model fits were nearly identical when the capillary pressuresaturation and relative
permeabilitysaturation relations were decoupled, introducing four additional relative permeabilityfitting parameters.
These modeling results suggest that dynamic capillary
effects were particularly important to capturing the MSO
data.
[8] In this paper the influence of wettability variations on
dynamic effects in capillary pressure is explored through the
analysis of the results of MSO experiments, conducted on
treated sands characterized by different equilibrium contact
angles. MSO data are modeled with a numerical multiphase
flow simulator that includes dynamic effects [OCarroll
et al., 2005b]. Differences between experiments are evaluated in the context of a theoretical relationship between

[9] Although a single capillary tube does not adequately

represent the complexity of a real porous medium, relationships defined at the pore scale can provide insight into
processes that manifest as macroscale behavior, including
capillary pressure hysteresis [Morrow, 1976], forces acting
at fluid interfaces [Hassanizadeh and Gray, 1993], and
fluidfluid interfacial area [Cary, 1994]. Dahle et al. [2005]
used a model derived for a single capillary tube to provide
insight into dynamic effects in capillary pressure for a
constant equilibrium contact angle. They used the Washburn
equation [Washburn, 1921] to develop an analogous expression to equation 1, thereby elucidating possible relationships
between the damping coefficient (t) and properties of the
medium and fluids. This study follows the methodology of
Dahle et al. [2005] but employs a modified form of the
Washburn equation [e.g., Blake and De Coninck, 2004] to
incorporate dynamic contact angles and their relationship to
wettability.
[10] Capillary flow of two immiscible fluids in a single
cylindrical pore can be described by the Washburn equation
[Washburn, 1921]:


212 cos  81 l1 2 l2 dl1

;
DP
r
r2
dt

where DP is an externally applied pressure, r is the radius of

the capillary tube, g 12 is the interfacial tension between fluids
1 and 2,  is the contact angle (measured through fluid 1),
m1 and m2 are the viscosities of fluids 1 and 2, respectively,
and l1 and l2 are the lengths of the tube occupied by fluids 1
and 2, respectively, as shown in Figure 1. Fluid 1 is taken to
be the wetting fluid and fluid 2 the nonwetting fluid.
Equation 2 has been expressed in terms of the viscosities of
both fluids [Adamson, 1982] and can be simplified by
defining a lengthaveraged viscosity as


1 l1 2 l2
L

[Dahle et al., 2005], where L = l1 + l2 is the total length of

the capillary tube, to yield
DP


212 cos  8L dl
2
;
r
r
dt

where the subscript on l1 has been removed (i.e., l = l1).

Equation 4 is typically applied using a constant contact
angle, taken to be the static contact angle [Washburn, 1921;
Blake and De Coninck, 2004; Dahle et al., 2005; Ralston et al.,
2008]. However, equation 4 can also be applied using the
dynamic contact angle
DP





212 cos d 8L dl
dl
2
; d f
;
r
r
dt
dt

[Martic et al., 2003; Blake and De Coninck, 2004; Lee and

Lee, 2007]. Several relationships have been proposed for

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d = f (dl/dt,), based on hydrodynamic and molecular

kinetic approaches [e.g., Blake and Haynes, 1969; Hoffman,
1975; Voinov, 1976; Cox, 1986; Zhou and Sheng, 1990;
BrochardWyart and de Gennes, 1992].
[11] A general form of the relationship used in the hydrodynamic approach, which emphasizes energy dissipation
due to viscous effects in a wedge of liquid near the contact
line, is
3d

3m



LM
9Ca ln
Lm

[Blake, 2006], where Ca is the capillary number (Ca = Um1/

g 12), U is the velocity of the contact line (U = dl/dt), LM is a
macroscopic length scale, Lm is a microscopic length scale
that defines a slip length or cutoff length [Ralston et al.,
2008], and m is a microscopic contact angle typically taken
to be equal to the static contact angle.
[12] In the molecularkinetic approach, the movement of
the contact line is assumed to depend on the displacement of
fluid molecules between adsorption sites within the three
phase (fluidfluidsolid) region at the contact line [Brochard
Wyart and de Gennes, 1992]. The characteristic frequency
and distance between these displacements are used to define
a coefficient of contact line friction, which then relates the
dynamic contact angle and the contact line velocity
U

12 cos   cos d



[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

[Blake and De Coninck, 2004], where Dg*s is the specific

activation energy of wetting, l is the average distance
between displacements, kB is the Boltzmann constant, and
T is temperature. b = m1u1/l3 for gasliquid systems, and b =
m1m2u1u2/hl3 for liquidliquid systems, where u is the
molecular volume and h is Plancks constant (see Blake and
Haynes [1969] for further discussion of molecularkinetic
parameters). In the molecularkinetic approach, the microscopic contact angle changes with velocity and is equal to the
dynamic contact angle. Note that U = dl/dt < 0 for drainage
here, as l refers to the length of tube occupied by the wetting
fluid and d <  for drainage.
[13] Blake [2006] also summarized work by Brochard
Wyart and de Gennes [1992] who proposed the following
expression that combines both hydrodynamic and molecular
kinetic approaches:
U

12 cos   cos d

 :
61
LM
ln

d
Lm

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been recognized due, in part, to the ability of each model to

provide adequate fits to experimental data [Blake, 2006;
Ralston et al., 2008]. Equations 6, 7 and 9 have typically been
applied to gasliquid systems [e.g., Martic et al., 2003; Lunati
and Or, 2009], and little information is available concerning
the values of key parameters (e.g., LM, Lm, and z) for application to liquidliquid systems. However, equation 7 offers an
advantage for use in this study because the value of z has been
linked to wettability for use in gasliquid systems [Blake and
De Coninck, 2004] and may offer the opportunity for similar
links in liquidliquid systems. Ranabothu et al. [2005] found
that a molecularkinetic model was able to provide better fits
to experimental dynamic contact angle data when compared
to the hydrodynamic model for simple fluids (including
water). However, for polydimethylsiloxane oils, their results
suggested that neither the molecularkinetic nor hydrodynamic model adequately represented observed dynamic
contact angle behavior for the range of contact velocities
tested. Thus, although the molecularkinetic approach was
selected for the present study, the range of fluids to which it
can be applied is still a subject of investigation. A combination of equations 5 and 7 gives a modified Washburn equation
DP






212
 dl
8L dl
2
cos  
12 dt
r
dt
r

10

[e.g., Martic et al., 2003; Blake and De Coninck, 2004] and

rearrangement gives
dl

dt




2
8L 1
212 cos 
DP
 2
:
r
r
r

11

Similar expressions could be derived using other approaches

to describe the dynamic contact angle, but modifications
would be required to accommodate two liquids [e.g., Cox,
1986]. Although expressions to estimate z in liquidliquid
systems have not been established [Blake and De Coninck,
2004], expressions derived for gasliquid systems suggest
that z will be greater for systems characterized by smaller
equilibrium contact angles [Blake and De Coninck, 2004].
That is, systems with a smaller equilibrium contact angles will
experience greater resistance to movement of the contact line.
[14] Following the approach of Dahle et al. [2005],
equation 11 can be considered as a porescale analogue to the
continuumscale rate of change in saturation, as expressed
by manipulating equation 1
@sw

1 Pcd Pcs :
@t

12

Here Pcd is analogous to DP, Pcs is analogous to 2g 12cos/r,

and t is analogous to (2z/r + 8mL/r2) in equation 11. Note
that, for negligible contact line friction (z 0), t is analogous to 8mL/r2, as presented by Dahle et al. [2005]. For
nonnegligible contact line friction (z > 0), the analogy
suggests that t will be a function of not only porous media
(r), fluid (m), and scale (L) properties but also the strength of
interactions between the fluids and the solid (z).
[15] On the basis of the above discussion, a damping
coefficient for a single capillary tube is defined as

Equations 6, 7, and 9 have all been used to describe dynamic

contact angles; however, a single preferred approach has not
4 of 13

tube


2
8L
 2 :
r
r

13

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OCARROLL ET AL.: WETTABILITY EFFECTS IN CAPILLARY PRESSURE

Table 1. Fluid Properties

Property

Water
3

Density (kg/m )
Viscosity (Ns/m2)

999
1.12 103

PCE

1630
9.0 104

Munson et al. [1990].

Pankow and Cherry [1996].

Equation 13 is a new expression presented here to link

the previously presented equation 11 for capillary tubes
(developed through previously presented equations 25, 7,
8, and 10) to equation 1 used to model macroscopic porous
media. A relationship between z and  is required to
investigate the effect of wettability variations on t tube using
equation 13. Expressions for Dg*s in liquidliquid systems
are not available in the literature [Blake and De Coninck,
2004]. The work of adhesion [WA = g 12(1 + cos)] has
been successfully used to approximate Dg*s in gasliquid
systems [Blake and De Coninck, 2002] and is assumed here
to be a reasonable firstorder estimate for liquidliquid
systems. Blake and De Coninck [2002] do not report a
theoretical basis for equating Dg*s and WA but were able to
closely match experimental results using this assumption,
which provides empirical support for the use of this
assumption here. Substituting WA for Dg*s in equation 8
yields


12 1 cos 2
  exp
kB T

14

It is important to emphasize that equations 11 and 12 are

only analogous, and the units of t and t tube are not the
same. To facilitate the comparison of theoretical t tube
values with those calculated from the experiments presented
in section 4, dimensionless values of t tube/t tube( = 83) were
calculated using equations 13 and 14 and are presented in
Figure 2 for L/r = 1. Airwater values were calculated using
g 12 = 72 mN/m, u1 = 3.0 1029 m3, l = 0.36 nm [Blake
and De Coninck, 2002], T = 298 K, and m1 = m. PCEwater
values were calculated using g 12 = 47.5 mN/m [Demond and
Lindner, 1993], u1 = 3.0 1029 m3, u2 = 1.7 1029 m3, l =
0.55 nm, T = 298 K, m1 = m, and m2 = 0.0009 kg/ms [Pankow
and Cherry, 1996]. The values of u1 and u2 were approximated based on density and molecular weight, and the l value
of 0.55 nm used for the PCEwater calculations is the estimated size of a PCE molecule based on l3 u2 [Blake and
De Coninck, 2004]. A reference value of t tube( = 83) was
chosen to correspond to operative contact angles in the experiments conducted during this work, as discussed in
section 3.2. It is implicitly assumed that t tube/t tube( = 83)
will behave in a similar manner as t/t( = 83). The curves
in Figure 2 show that larger damping coefficients are
expected for smaller equilibrium contact angles. According
to equation 1, larger damping coefficients will result in
greater dynamic effects in capillary pressure. This analysis
suggests that t values in waterwet systems (approaching
 = 0) could differ by an order of magnitude when compared to intermediatewet systems (approaching  = 90).
[16] It is important to note that the magnitude of the
t tube/t tube( = 83) value in Figure 2 is sensitive to the
choice of l, the value of which is not clear for liquidliquid
systems [Blake and De Coninck, 2004]. For example, using

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a l value based on water instead of PCE changes the

maximum t tube/t tube( = 83) value for PCEwater from
approximately 22.1 to 3.7. Similarly, t tube/t tube( = 83) is
also sensitive to L/r. For example, increasing L/r by an order
of magnitude lowered the maximum t tube/t tube( = 83)
value for PCEwater from 22.1 to 21.8 and for airwater
from 5.2 to 2.1.

3. Materials and Methods

3.1. Fluids and Porous Media
[17] All MSO and equilibrium experiments were conducted using laboratory grade (99%) tetrachloroethene (PCE)
(Aldrich Chemical, Milwaukee, WI) and MilliQ water, with
properties listed in Table 1. The columns for all MSO and
equilibrium experiments were packed with a mixture of F35
F50F70F110 Ottawa sand (US Silica, Ottawa, IL), with a
mean grain size of 0.026 cm, and a uniformity index of 2.79
[OCarroll et al., 2005a]. The same sand was used by
OCarroll et al. [2005b] to investigate dynamic effects in
capillary pressure in waterwet sand.
[18] A batch of the sand was treated with a 5% (by volume)
solution of octadecyltrichlorosilane (OTS) (ICN Biomedicals
Inc, Aurora, OH) in ethanol [Anderson et al., 1991]. Two
additional batches of the sand were treated by immersing the
sand in a 5% (by volume) solution of Rhodorsil Siliconate
51T (RDS) (Rhodia Silicones, Rock Hill, SC) in MilliQ
water and lowering the pH below 8 [Fleury et al., 1999]. The
two batches of RDStreated sand were prepared separately
(referred to here as batches A and B), which may have resulted in the development of different surface properties, as
discussed in section 4.1.
[19] The wetting conditions produced by the OTS and
RDS treatments were evaluated by OCarroll et al. [2005a]
by measuring advancing and receding contact angles on
smooth quartz slides (Fisher Scientific, Pittsburg, PA) treated
using the same procedures used for the sands. The contact
angles were measured using the axisymmetric drop shape
analysis technique [Cheng et al., 1990; Lord et al., 1997] as
described by OCarroll et al. [2005a]. The measured values
of the water receding contact angles are listed in Table 2.
These measured contact angles suggest that the OTS treatment produced an organicwet surface on the slides, and the
RDS treatment produced an intermediatewet surface on the

Figure 2. Dimensionless damping coefficient for a single

capillary tube as a function of the equilibrium contact angle
for airwater and PCEwater systems.

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Table 2. Contact Angles Measured Through the Aqueous Phasea

Treatment

Receding
Contact
Angle on
Glass Slideb

Rhodorsil Siliconate 51T (RDS)

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)

Standard deviation in parentheses.

OCarroll et al. [2005a].
c
Interfacial tension was equivalent in all systems (41 mN/m).
d
Calculated by scaling waterwet PcS fit to match EQRDSA data.
e
Calculated by scaling waterwet PcS fit to match EQRDSB2 data
[OCarroll et al., 2005a].
b

slides according to the contact angle classification of

Morrow [1976].
3.2. Equilibrium Drainage Experiments
[20] Four equilibrium drainage experiments were conducted: one using RDStreated sand from batch A, two
using RDStreated sand from batch B, and one using
OTStreated sand, referred to here as EQRDSA, EQRDS
B1, EQRDSB2, and EQOTS, respectively. Results from
EQRDSB2 were previously reported by OCarroll et al.
[2005a]. The replicate experiments EQRDSB1 and EQ
RDSB2 were performed on subsamples of the same treated
sand but represent different packings. Primary drainage
capillary pressuresaturation data were measured using a
pressure cell system based on the design of Salehzadeh and
Demond [1999]. Dry sand from the OTS or RDS batches
were packed into a column (length = 1.27 cm and ID = 2.54 cm),
flushed with carbon dioxide, and flushed with 200 pore
volumes of deaired MilliQ water to begin each experiment
at 100% water saturation [OCarroll et al., 2005a]. The sands
in each of the equilibrium drainage experiments were subsamples of the sands used in the MSO experiments, to facilitate comparison between the results obtained using the small
pressure cell system and those from the larger MSO columns.
[21] An operative contact angle was calculated using
Leverett scaling for each of the equilibrium drainage experiments. The operative contact angle is defined as the contact
angle required to scale the van Genuchten PcS curve, fit to
waterwet (i.e.,  = 0) sand data, to measured drainage data
for the treated sands. van Genuchten model parameters and
operative contact angles were fitted by minimizing the
square difference between measured and fit water saturation
at a given capillary pressure. These operative contact angles
represent equilibrium receding contact angles that are characteristic of each porous medium and include the effects of
both the OTS or RDS treatment and the porous medium
surface. In this work, all drainage curves were fit with van
Genuchten [1980] PcS expressions [OCarroll et al., 2005b].
3.3. Multistep Outflow (MSO) Experiments
[22] Three MSO experiments were conducted: one using
RDStreated sand from batch A, one using RDStreated sand
from batch B, and one using OTStreated sand, referred to
here as MSORDSA, MSORDSB, and MSOOTS,
respectively. The experiments were conducted using the
approach described by OCarroll et al. [2005b]. Dry sand

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from the OTS or RDS batches was packed into a custom

designed aluminum column (length = 9.62 cm and ID =
5.07 cm), flushed with carbon dioxide, and then flushed
with a minimum of 30 pore volumes of deaired MilliQ
water to completely saturate the column. PCE flowed from a
constant pressure reservoir into the bottom of the column
through a PCEwet PTFE membrane (0.45 mm pore size;
Pall Corporation, Ann Arbor, MI), displacing water from the
top of the column through a waterwet nylon membrane
(0.45 mm pore size; Pall Corporation, Ann Arbor, MI) and
into a reservoir with an overflow weir.
[23] Fluid flow was induced by imposing a fixed air
pressure above the PCE in the constant pressure reservoir.
Water and PCE pressures were measured in the top and
bottom column end plates, respectively, using pressure
transducers (MicroSwitch, Freeport, IL). The PCE pressure
was increased in a series of steps (between 1.0 and 8.6 cm
H2O) during each experiment; 9 steps were used in MSO
RDSA, 4 steps in MSORDSB, and 10 steps in MSO
OTS (Table 3). Steady state was not necessarily achieved
prior to the initiation of subsequent steps. Each experiment
was stopped when additional pressure increases did not
result in significant additional water outflow, at which point
it was assumed that residual water saturation had been
achieved.
3.4. Numerical Model
[24] A 1D, fully implicit, pointcentered, fully coupled
finite difference multiphase flow simulator was used to
analyze the MSO experimental results [OCarroll et al.,
2005b]. The development of the model is discussed by
OCarroll et al. [2005b], and essential elements are presented

Table 3. Pressure Steps Employed During MSO Experiments

PCE Pressure Change in PCE ColumnAveraged
at Bottom
Reservoir
Effective Water
of Column
Pressure
Saturation at Start
Step No. Time (h)
(cm H2O)
(cm H2O)
of Pressure Step
MSORDSA
1
0
2
0.1
3
0.5
4
12.4
5
16.1
6
38.8
7
45.3
8
61.5
9
66.2
MSORDSB
1
0
2
0.03
3
22.3
4
33.9
MSOOTS
1
0
2
0.7
3
4.1
4
16.8
5
25.6
6
27.4
7
40.3
8
41.6
9
42.5
10
43.1

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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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Table 4. Numerical Model Parameters

Parameter
Input parameters
Sand permeability at Sw =1 (m2)
Nylon membrane permeability at Sw =1 (m2)
Teflon membrane permeability at Sw =Sr (m2)
Porosity
Fitting parameters and RMSE (t = 0)
a (cm H2O)1
n
Sr
RMSEQ
RMSES
Fitting parameters and RMSE (t 0)
a (cm H2O)1
n
Sr
A (kg/ms)
RMSEQ
Reduction in RMSEQ compared to t = 0 fit (%)
RMSES

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

here for clarity. The governing equation for the aqueous

phase is









@
w @Pw
@Sw @Pcs
@
@Pw
w

w s


w g ;
Sw
@z
@Pw @t
@Pc @t
@z

15

where is porosity, rw is water density, lw = kw/mw is

water mobility, mw is the water viscosity, kw = kkrw is the
water permeability, k is the intrinsic permeability, krw is
the water relative permeability, g is gravity, and z is the spatial
dimension. In the governing equation for the NAPL phase,
the NAPL phase pressure is expanded in terms of the aqueous
phase and dynamic capillary pressures (Pn = Pdc + Pw).
Defining Pdc using equation 1 gives an expression in terms
of Psc and Pw






@
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

where rn is NAPL density, Sn is NAPL saturation, ln = kn/mn

is NAPL mobility, mn is the NAPL viscosity, kn = kkrn is the
NAPL permeability, and krn is the NAPL relative permeability. In this expansion, dynamic effects in the NAPL
compressibility term are ignored. Static capillarysaturation
relations were represented by a van Genuchten [1980] PcS
function (VG)
Pcs

1=n
1  1=m
Se  1
;


where m = 1 2/n. The relative permeabilitysaturation

expressions were not varied as a function of system wettability during this study. The appropriateness of this approach
was confirmed by observing that use of wettabilitymodified
relatively permeability functions for the MSOOTS experiment had a very minor impact on the magnitude of the
damping coefficient estimated through inverse modeling
(further discussed in section 4.4).
[25] The damping coefficient (t) has sometimes been
treated as a constant for the modeling of dynamic effects [e.g.,
Hassanizadeh et al., 2002]. However, it is widely believed
that t = t(Sw) [Hassanizadeh et al., 2002; Dahle et al., 2005;
Manthey et al., 2005; OCarroll et al., 2005b; Berentsen
et al., 2006; Mirzaei and Das, 2007], although the form of
this function remains under investigation [Berentsen et al.,
2006]. In this study the following functional form was
assumed [OCarroll et al., 2005b]:

17

where a, m, and n are the van Genuchten model parameters,

Se = (Sw Sr)/(1 Sr) is the effective water saturation, and Sr
is the residual water saturation. Relative permeability was
expressed by the Burdine [1953] relationship
h

m i
and
krw Se2 1  1  Se1=m

18

h
im
krn 1  Se 2 1  Se1=m ;

19

20

where the constant A is a fitting parameter. The use of

equation 20 was previously found to significantly improve
the ability of the numerical simulator to fit outflow data from
MSO experiments in waterwet media compared to the use
of a constant t value [OCarroll et al., 2005b]. Although
experimental studies support the use a saturation dependent
t [e.g., Manthey et al., 2004; Sakaki et al., 2010], the
assumption of a linear form needs further study.
[26] The MSO experiments were simulated using a column domain discretized with 145 nodes in a variable grid
spacing. A maximum grid spacing of 103 m was located at
the center of the domain, and a minimum grid spacing of 8
106 m was located near the column boundaries. A dynamic
time step adjustment algorithm was employed using time
steps between 1012 and 10 s.
[27] Best fits to observed data were obtained by varying
three parameters (Sr, a, and n) for the t = 0 simulations and
four parameters (Sr, a, n, and A) for the t 0 simulations to
minimize the rootmeansquare error based on the difference
between measured and predicted values of the cumulative
water outflow (RMSEQ). The PcS parameters derived from
fitting the MSO data were then used to generate PcS curves
for comparison to PcS data obtained from independent

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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].

4. Results and Discussion

4.1. Equilibrium Drainage Experiments
[28] Capillary pressure/saturation data from the four equilibrium drainage experiments are shown in Figure 3, along
with data from an equivalent experiment previously conducted in the same size fraction of waterwet sand [OCarroll
et al., 2005b], referred to here as EQWW. Experiments
with the RDS and OTStreated sands exhibited decreased
capillary pressures at all effective saturation values, compared to those in the waterwet sand. This decrease in capillary pressure, at a given water saturation, is consistent with
other experiments conducted on nonwaterwet material
[e.g., Morrow, 1976; Anderson, 1987a; Bradford and Leij,
1995; Bradford et al., 1997; Ustohal et al., 1998; OCarroll
et al., 2005a; Hwang et al., 2006] and supports the expectation that less energy, characterized by the area under the
PcS curve [Leverett, 1941], is required for drainage in such
materials [Donaldson and Alam, 2008]. Capillary pressure/
saturation data for the two RDS treatments are distinctly

different. Sands from these two experiments were from

different batches leading to these observed differences.
Because the same sand treatment procedure was used for
both batches, it is unclear why each batch yielded differing
wettability behavior. For the treatments used in this study,
the OTStreated sand had the largest operative contact angle
(Table 2). This is qualitatively consistent with the contact
angles measured on glass slides, where the OTStreated
slides also exhibited the largest contact angle. However,
fitted contact angles exhibit two important discrepancies
with those measured on glass slides. First, the operative
contact angle for the OTStreated sand falls within the range
for an intermediatewet system (i.e., 60 <  < 130) rather
than the NAPLwet system (i.e.,  > 130) that was suggested by the glass slide measurement. This discrepancy was
previously noted by OCarroll et al. [2005a], who stated that
the operative contact angle of  90 was consistent with
the negligible capillary pressure behavior observed during the
infiltration of PCE into OTStreated sand [OCarroll et al.,
2004]. In OCarroll et al. [2004], use of an operative contact angle greater than 90 for OTStreated sand in the
numerical simulator led to results that were inconsistent with
experimental sandbox behavior. Second, the two separate
RDS treatments (A and B) did not produce similar operative
contact angles; treatment B produced an operative contact
angle similar to the OTS treatment. As discussed above, the
cause of the discrepancy in operative contact angles between
the two separate RDS treatments is unknown.
4.2. Multistep Outflow (MSO) Experiments
[29] The outflow response from the three MSO experiments is shown in Figure 4 as cumulative outflow (Q)

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conditions. While the achievement of Q/t 0 is not

required for the determination of PcS parameters by inverse
modeling, its attainment facilitates the direct comparison
among MSO experiments by allowing the normalization of
the outflow as described below. The effective water saturations, and those listed in Table 3, are columnaveraged
values based on the cumulative outflow during the experiment. The selected outflow responses (Figure 5) have been
shifted such that t = 0 corresponds to the initiation of the
pressure step (referred to here as relative time), and normalized to the cumulative change in outflow, such that the
initial normalized outflow is zero, and the final normalized
outflow is 1, or
QN

Figure 4. Data from the multistep outflow experiments

(symbols) compared to best fit numerical simulations (lines)
assuming (a) no dynamic effects and (b) dynamic effects
described by equations 1 and 20. The measured data in
Figures 4a and 4b are the same, and only selected data
points (approximately every 60th point) have been plotted
for clarity.
versus time. Although the results from MSORDSB appear
to have resulted from a single pressure step, four pressure
steps were used. The majority of the water outflow occurred
during the second step, with the next step being initiated
22.3 h into the experiment (Table 3). Each of the experiments exhibits an initially rapid increase in outflow, followed by a slower approach to zero outflow (i.e., steady
cumulative outflow), subsequent to each step change in the
PCE boundary pressure. Previous studies of waterwet
media have shown that the slow approach to zero outflow is
indicative of dynamic effects in capillary pressure if the
relative permeability to each phase is not small (i.e., at
intermediate fluid saturations) [OCarroll et al., 2005b].
[30] Direct comparisons of the approach rate to zero
outflow among the MSO experiments is not easily accomplished using Figure 4 due to the different magnitudes of the
pressure steps, the different magnitudes of the outflow
response produced, and the different water saturation conditions when the pressure steps were initiated. To facilitate a
comparison of the experimental data, the outflow response
from one pressure step in each experiment was chosen. The
outflow responses selected were those that achieved near
steady cumulative outflow (Q/t 0) before the initiation
of the next pressure step and took place at effective water
saturations of Se 0.4 to Se 0.8. On the basis of these
criteria, the selected curves represent reasonably similar

Q  Qi
;
Qf  Qi

21

where QN is the normalized cumulative outflow, Q is the

cumulative outflow at any time, Qi is the cumulative outflow
at the initiation of the pressure step, and Qf is the cumulative
outflow immediately prior to the initiation of the next
pressure step. In addition to the MSO experiments conducted in this study, selected outflow responses from water
wet experiments (referred to here as MSOWWA and
MSOWWB) [OCarroll et al., 2005b] are also plotted in
Figure 5 for comparison. The outflow step selected from
MSOWWA (step 4) resulted from a PCE pressure change
of 6.84 cm of water and produced a decrease in effective
water saturation from 0.48 to 0.14. For MSOWWB, the
selected step (step 6) resulted from a PCE pressure change
of 4.53 cm of water and produced a decrease in effective
water saturation from 0.73 to 0.52.
[31] The scaled outflow curves in Figure 5 reveal that zero
outflow was approached faster in the experiments with the
OTStreated sand than with the waterwet sand. This faster
approach is consistent with a decrease in dynamic capillary
pressure effects associated with a larger equilibrium contact
angle, as discussed in section 2. However, it could also be
attributed to an increase in relative permeability, as larger
contact angles allow the drainage of water through larger
pores. The outflow response in the RDStreated sand varied
considerably between the experiments conducted using
material from batches A and B. The response in MSORDS
A was similar to the waterwet experiments, but the response
in MSORDSB was similar to the experiments with OTS
treated sand. The similar behavior of the MSORDSB and
MSOOTS experiments is consistent with their similar
equilibrium drainage PcS curves (Figure 3) and the correspondingly similar operative contact angles of 82.3 and
83.4, respectively. The faster response in MSORDSB and
MSOOTS is consistent with the theory presented in section
2, where decreased dynamic effects are expected for systems
characterized by larger equilibrium contact angles.
4.3. Numerical Simulations
[32] The MSO experimental data were first fit using the
model described in section 3.4, using the van Genuchten
Burdine PcSkr relationships, and t = 0 (i.e., no dynamic
capillary pressure effects). This is representative of the
conventional approach for modeling multiphase flow, where
Psc is achieved instantaneously following a disturbance to a
system at equilibrium [Hassanizadeh and Gray, 1993]. The
best fit simulation results for the t = 0 case are plotted in

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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-

tions and increase the importance of data in the intermediate

effective water saturation range [OCarroll et al., 2005b].
The VG PcS functions based on fits to the MSO data using
t = 0 were generally consistent with the static PcS measurements, despite the inability of the multiphase flow
simulator to fit the outflow data using t = 0. Note that, in the
equilibrium capillary pressure/saturation experiments, large
decreases in water saturation were observed following a small
increase in capillary pressure, when the operative contact
angle was large. The VG PcS curves generated from the
MSO approach, however, do not conform to these abrupt
changes in water saturation following small increases in
capillary pressure. Nevertheless, the saturation levels at
higher capillary pressures are consistent with the static
measurements. Thus, this analysis indicates that PcS functions fit using MSO data without considering dynamic
effects in capillary pressure can yield PcS curves that are
in good agreement (i.e., similar capillary pressure at 50%
effective water saturation) with independent PcS experiments for a broad range of wettability conditions.
[34] MSO experimental data were next fit using the same
approach as described above (i.e., fitting VG parameters a
and n as well as residual water saturation) and assuming t 0
(equation 20) to investigate whether dynamic effects could
improve the fit. The best fit simulation results are plotted in
Figure 4b, and the best fit values of the parameters are listed
in Table 4. The inclusion of t as a linear function of Se
significantly improved the fits to the MSO data. The
RMSEQ values for MSORDSA, MSORDSB, and MSO
OTS decreased by 62%, 42%, and 33%, respectively. In
addition, the simulation results provided much better fits
to the approach to zero outflow and the magnitude of the
steady cumulative outflow (Figure 4b). Previous work
demonstrated that a modeling approach that decoupled the
capillary pressure and relative permeability constitutive
relationships, adding three additional fitting parameters,

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produced nearly identical agreement between the numerical

model and experimental MSO data [OCarroll et al., 2005b].
Thus, this alternative modeling approach was not considered
herein.
[35] Only relatively small differences exist between the fit
values of the PcS function parameters for t = 0 and t 0
(Table 4). The resulting PcS curves are similar to those
shown in Figure 3 and, thus, a separate set of curves is not
shown. These results demonstrate that the static PcS data
can also be well matched using the fit parameter values
based on t 0 simulations, as indicated by the similar
RMSES values calculated for the t = 0 and t 0 parameter
fits (Table 4).
4.4. Effect of Contact Angle on the Damping
Coefficient (t)
[36] The RMSEoptimized A values differed significantly
among experiments (Table 4). MSORDSA, characterized
by the lowest operative contact angle of these experiments,
had a RMSEoptimized value of A = 3.43 107 kg/ms.
This lies between the values of A = 5.64 107 kg/ms and
A = 1.99 107 kg/ms reported for waterwet material
[OCarroll et al., 2005b]. The MSORDSB and MSOOTS
experiments, with higher operative contact angles, had
RMSEoptimized values of A = 2.76 106 kg/ms and A =
3.74 106 kg/ms, respectively.
[37] It is important to examine whether discrepancies
between observed and simulated cumulative water outflow
can be attributed in part to the selected relative permeability
functions, which determine the rate of fluid flow and,
therefore, the transient drainage of a twofluid system. The
selection of wetting and nonwetting fluids used to assign
these relative permeability functions becomes increasingly
ambiguous as a system approaches an operative contact
angle of 90, as was the case for the OTS and RDSB
experiments. It is possible that the faster approach to steady
state observed in these experiments, and the correspondingly
smaller t values, were due in part to the increased permeability of the treated sand to NAPL, associated with the
increased operative contact angle. To test the sensitivity of
the A values to the relative permeability expressions used in
the multiphase flow simulator, the MSOOTS experiment
was also simulated with the wettability of the fluids reversed.
That is, water permeability was calculated using the nonwetting phase relative permeability expression (equation 19),
and the NAPL permeability was calculated using the wetting
phase relative permeability expression (equation 18). This is
expected to bound the dynamic behavior, based upon theoretical [e.g., Bradford et al., 1997] and experimental [e.g.,
Anderson, 1987b] work that has shown that water relative
permeability tends to increase and NAPL relative permeability to decrease as wettability changes from waterwet to
NAPLwet. Results of simulations employing this relative
permeability reversal revealed that the new RMSEoptimized
value of A = 1.83 106 kg/ms was not significantly different,
based on a 95% confidence limit, from the former value of
A = 3.74 106 kg/ms. This result demonstrates that the
choice of wetting fluid did not affect the magnitude of t
determined using the simulations.
[38] The t values, based on equation 20 and the A values
in Table 4, for MSORDSA (operative contact angle of
64.4), and those of the two previously reported waterwet

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sand experiments, are an order of magnitude greater than

those for MSORDSB and MSOOTS (operative contact
angles of 82.3 and 83.4, respectively). This trend is consistent with the values presented in Figure 2 for a PCEwater
system, where t tube/t tube( = 83) increases as the system
becomes more water wetting. Here it is expected that t tube/
t tube( = 83) behaves in a similar manner as t/t( = 83).
While the observed increase in t with decreasing equilibrium contact angle is consistent with Figure 2, the small
difference between the t values for MSORDSA and the two
previously waterwet sands is not. For example, based on the
operative contact angles and trends presented in Figure 2,
t values for MSORDSA should be approximately 3
times larger than the t values for MSORDSB and MSO
OTS [ = 64.4, t tube/t tube( = 83) = 3.0] and approximately 4 times less than those in the waterwet system [ =
34.4, t tube/t tube( = 83) = 11.9]. This suggests that while
the capillary tube model provides qualitative insight, it is
insufficient to provide a quantitative analogy to actual porous
media in this context. Overall, however, the increase in
experimentally determined t values with decreasing equilibrium contact angle is consistent with the conceptual model
presented in section 2 and the expectation of increased
dynamic capillary pressure effects with decreased equilibrium contact angle.

5. Summary and Conclusions

[39] A series of MSO experiments conducted in 1D
columns was used to explore the influence of wettability on
dynamic effects in capillary pressure. These effects were
qualitatively compared to a theoretical model based on the
consideration of dynamic contact angles during interface
movement in a single capillary tube. The dynamic response
in the cumulative column outflow was found to be faster in
experiments in an OTStreated sand, characterized by a
higher operative contact angle, than in experiments conducted in waterwet or RDStreated sands. As has been
reported for waterwet sands [OCarroll et al., 2005a], a
numerical model using traditional constitutive relationships,
which neglect dynamic effects (t = 0), failed to adequately
fit the dynamic outflow data. However, the discrepancy was
less pronounced in experiments using RDS and OTS sand
with higher operative contact angles. Despite the poorer
representation of outflow data when assuming t = 0, PcS
function parameters estimated through inverse modeling
were consistent with equilibrium experiments, regardless
of wettability. Including dynamic effects in the numerical
simulations, using a damping coefficient that is a linear
function of effective water saturation (t = ASe + A), greatly
improved the numerical fit to the measured MSO outflow
data. These fits yielded damping coefficient values for
material with equilibrium contact angles greater than 80
that were an order of magnitude less than those for material
with equilibrium contact angles less than 65.
[40] The MSO experiment results reported here show that
an increased equilibrium contact angle produced a faster
approach to steady state during drainage, a reduced discrepancy between observed and simulated outflow values
using t = 0 and smaller t values as a function of saturation.
These previously unreported effects are consistent with the
model presented here based on interface movement in a
single capillary tube, which predicts increased damping

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OCARROLL ET AL.: WETTABILITY EFFECTS IN CAPILLARY PRESSURE

coefficients with decreasing equilibrium contact angle

based on dynamic contact angles. While the consideration of
dynamic contact angles alone does not explain all observations related to dynamic capillary pressure effects, this
model does help to explain observations of this study related
to wettability. These results suggest that dynamic effects in
capillary pressure are likely not only a function of material,
fluid, and scale properties but also depend on the interaction
of the fluids and solid and that this interaction may be largely
responsible for localscale dynamic capillary pressure effects.
Furthermore, the theoretical and experimental results presented here suggest that it may be possible to neglect
dynamic effects in systems that approach intermediate
wetting conditions but that they will be increasingly
important for more waterwet systems. The understanding
of dynamic effects in capillary pressure and the implications
of including those effects in numerical simulators would
benefit from additional experiments in materials of differing
wettability, theoretical t expressions that incorporate wettability at the REVscale (e.g., application of the molecular
kinetic approach at the macroscopic scale and developing a
functional relationship between t(Sw) and operative contact
angle), and fieldscale simulations that include dynamic
effects.
[41] Acknowledgments. This research was supported by grant DE
FG0796ER14702, Environmental Management Science Program, Office
of Science and Technology, Office of Environmental Management, U.S.
Department of Energy (DOE), and by the Natural Sciences and Engineering
Research Council (NSERC) of Canada through a Strategic Grant (OCarroll/
Gerhard) and a Postdoctoral Fellowship (Mumford). Any opinions, findings,
conclusions, or recommendations expressed herein are those of the authors
and do not necessarily reflect the views of the DOE or NSERC.

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L. M. Abriola, School of Engineering, Tufts University, 105 Anderson
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J. I. Gerhard and D. M. OCarroll, Department of Civil and Environmental
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K. G. Mumford, Department of Civil Engineering, Queens University,
Kingston, ON K7L 3N6, Canada.

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