WATER RESOURCES RESEARCH, VOL. 43, W08409, doi:10.

1029/2006WR005418, 2007

Subsurface contaminant transport in the presence of colloids:

Effect of nonlinear and nonequilibrium interactions
Hesham M. Bekhit1,2 and Ahmed E. Hassan1,2
Received 10 August 2006; revised 26 March 2007; accepted 7 May 2007; published 9 August 2007.
[1] The effect of kinetic nonlinear sorption of contaminants in the presence of colloids is
the focus of this study. Different sorption isotherms are considered where contaminant
sorption and colloid deposition are assumed to be linear or nonlinear (Freundlich), and
contaminant attachment to mobile and immobile colloids is assumed to follow either linear
or Langmuir isotherms. Varying combinations accounting for different possibilities are
used to investigate effects of different isotherms on contaminant transport. Two-
dimensional numerical simulations in homogenous media show that the effect of colloids
on nonlinearly sorbing contaminant is altered from facilitation to retardation depending on
the Freundlich exponent and concentration value. One finding from the study indicates
that incorporating the colloid effect on contaminant transport does not necessarily
represent a conservative assumption. The study shows that ignoring the fact that colloids
have limited sites and describing contaminant attachment to colloids by linear isotherms
may lead to inaccurate results. In addition, it is found that assuming colloids are
linearly deposited on the solid matrix is a conservative assumption in the applications that
focus on peak concentration arrival. However, when small contaminant concentrations are
of concern (i.e., early arrival is the quantity of interest), assuming nonlinear colloidal
deposition becomes the critical scenario.
Citation: Bekhit, H. M., and A. E. Hassan (2007), Subsurface contaminant transport in the presence of colloids: Effect of nonlinear
and nonequilibrium interactions, Water Resour. Res., 43, W08409, doi:10.1029/2006WR005418.

1. Introduction nonlinear sorption behavior to linear sorption leads to

[2] Analytical and numerical modeling of reactive con-
taminant transport in subsurface environments has been an
active area of research for decades. The studies on contam-
inant sorption and desorption have evolved from using a
simple retardation factor based on equilibrium assumptions
to incorporating kinetic reactions. These studies were con-
ducted by incorporating different sorption sites with varying
characteristics and using a variety of expressions character-
izing physical and chemical nonequilibrium [Sardin et al.,
1991]. Through a large body of analytical and numerical
modeling studies, solutions were devised for the reactive
contaminant transport problem under linear equilibrium and
nonequilibrium (kinetic) conditions. Sardin et al. [1991]
provide a detailed review of studies focused on modeling
nonequilibrium transport of linearly sorbing solutes in
porous media.
[3] Modeling reactive chemical transport of contaminants
experiencing nonlinear equilibrium or kinetic reactions has
received little attention as compared to linear reactions.
Studies that consider nonlinear interaction show agreement
over the importance of the nonlinear sorption processes.
These studies concluded that simplifying the effect of
1
Irrigation and Hydraulics Department, Faculty of Engineering, Cairo
University, Orman, Giza, Egypt.
2
Division of Hydrologic Sciences, Desert Research Institute, Las Vegas,
Nevada, USA.
Copyright 2007 by the American Geophysical Union.
0043-1397/07/2006WR005418
significant errors in predicting travel distance and could
produce misleading results. Because of nonlinearity in the
sorption process, the amount of contaminant sorbed onto the
solid matrix highly depends on the concentration value of
dissolved contaminant where larger concentrations exhibit
different sorption and retardation than do smaller concen-
trations. On the basis of the nonlinear factor, the portion of
the plume with high concentration exhibits more or less
retardation than the portion having lower concentration.
[4] Several studies revealed the importance of the non-
linear behavior of the contaminant [van Genuchten and
Cleary, 1982; Bolt, 1982]. One of the examples is the work
presented by Weber et al. [1991] who studied the effects of
nonlinearity on plume shape. They concluded that the
velocity of the center of mass of a contaminant plume
experiencing nonlinear sorption is significantly lower than
that of a linearly reacting plume. In addition, Serrano
[2003] studied the propagation of nonlinear reactive con-
taminants in porous media. His results indicated that non-
linear reactions may have a significant effect on the shape
and spatial distribution of a contaminant plume at any given
time.
[5] This study investigates the role of nonlinear sorption
on contaminant transport in the presence of colloids. Rec-
ognition that colloids might be important in facilitating
transport of contaminants arose from studies demonstrating
that strongly sorbing contaminants could travel much fur-
ther and faster than anticipated from traditional solute
transport models [McCarthy and McKay, 2004]. For exam-
ple, at the Nevada Test Site, strongly sorbing radionuclides

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
were observed in groundwater at large distances outside
nuclear detonation cavities [Coles and Ramspott, 1982;
Buddemeier and Hunt, 1988; Kersting et al., 1999]. Like-
wise, enhanced transport of radionuclides at Chalk River
Nuclear Laboratories in Canada [Walton and Merritt, 1980;
Champ et al., 1984], Oak Ridge National Laboratory in
Tennessee [McCarthy et al., 1998a, 1998b], and a U deposit
in Australia [Short et al., 1988] were attributed to associ-
ation of the contaminants with a mobile colloidal phase. In
addition, at two separate sites at Los Alamos, New Mexico,
plutonium and americium were detected at much greater
distances from the source than predicted by dual porosity
transport models [Nelson and Orlandini, 1986].
[6] These findings compelled researchers to develop
transport models that account for colloid-facilitated contam-
inant transport. These models suggest that depending on
system conditions, the presence of colloids in porous media
may either enhance or retard contaminant transport [e.g.,
Grindrod, 1993; Smith and Degueldre, 1993; Abdel-Salam
and Chrysikopoulos, 1995a, 1995b; Ibaraki and Sudicky,
1995a, 1995b; Baek and Pitt, 1996; Cvetkovic, 2000;
Marseguerra et al., 2001a, 2001b; Ren and Packman,
2004, 2005; Bekhit and Hassan, 2005a; Bekhit et al., 2006].
[7] For colloid-facilitated transport to represent an im-
portant process in the subsurface, colloids must be present
in sufficient quantities in the porous medium and must
remain in suspension for sufficiently long times. Grolimund
and Borkovec [2004] describe a scenario of this process. A
natural porous medium is saturated with monovalent cations
at first. Then, the medium is infiltrated with water of low
ionic strength. Under these conditions a considerable
amount of colloidal particles is released from natural porous
media and remains suspended [Grolimund and Borkovec,
1999; Grolimund et al., 2001]. The sudden change in water
chemistry (e.g., ionic strength) was also shown to cause a
rapid release of colloidal particles that were attached to the
solid matrix [Roy and Dzombak, 1998]. This scenario
results in high colloid concentration and may be encoun-
tered in real field situations.
[8] Grolimund and Borkovec [2004] mention two realis-
tic situations, where colloid release is likely. The first
situation concerns an aquifer which is in contact with
seawater and is infiltrated with freshwater. The second
situation concerns a soil or an aquifer saturated with a
dump site leachate (typically dominated by monovalent
cations), and is then infiltrated with rainwater or ground-
water of low salinity. In both situations, a normality front
develops, within which the salinity of the pore water drops
substantially. Just after the normality front, colloids will be
released from the solid matrix [Grolimund and Borkovec,
2004]. If the aquifer is contaminated with strongly sorbing
contaminants, they will be transported by the released
colloids. The importance of colloid-facilitated transport in
this situation has been demonstrated by means of laboratory
column experiments [Grolimund et al., 1996; Roy and
Dzombak, 1998; Saiers and Hornberger, 1996, 1999; Faure
et al., 1996; Flury et al., 2002] and in the field [Kersting et
al., 1999].
[9] When looking at colloids and their effect on subsurface
transport, two classes of studies can be distinguished. The
first class focuses on transport of colloidal particles and their
interaction with the solid matrix in groundwater systems. The
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W08409
second class of studies focuses on colloid-facilitated contam-
inant transport where interactions between colloids, contam-
inants, and solid matrix are studied. Numerous studies in each
of the two classes have been reported for saturated porous
media, fractured media, and also unsaturated media. We
review in the following some of the experimental and
numerical studies reported in the two categories with empha-
sis on saturated porous media studies.
[10] Examples of laboratory studies in the first class
include the work of Mills et al. [1991] who summarized
modeling approaches developed for colloid transport and
presented a test model for porous media. Bradford et al.
[2002] conducted saturated soil column experiments to
explore the influence of colloid size and distribution of soil
grain size on the transport of colloids in saturated porous
media. The results presented by Bradford et al. [2002]
showed that effluent colloid concentrations and spatial
distribution of colloids attached to porous media highly
depend on colloid size and distribution of soil grain size.
Peak effluent concentrations decreased and surface mass
retained by the porous media increased when the colloid
size increased and the median soil grain size decreased.
[11] Experimental results of other studies showed that
dissolved organic matter and other types of colloids dem-
onstrate a high affinity for the solid matrix [Saiers and
Hornberger, 1999; Saiers et al., 1994; Dunnivant et al.,
1992; Knabner et al., 1996; Corapcioglu and Choi, 1996].
One of the main findings produced from these experiments
showed that colloids are reactive, and their transport could
be predicted using the advection-dispersion equation and
simulating the deposition process by an equilibrium iso-
therm, a first-order kinetic process or, more complicated,
nonlinear kinetics.
[12] Sirivithayapakorn and Keller [2003] conducted
experiments to simulate colloid transport in saturated porous
media. They focused on studying the effects of excluding
colloids from areas having small pore sizes. They found that
the size exclusion phenomenon occurred when the ratio of
pore throat to colloid diameter was less than 1.5.
[13] Different mathematical models were developed to
describe colloid transport in the subsurface. Johnson and
Elimelech [1995] accounted for the possible occurrence of
blocking, where they presented a model containing dynamic
blocking functions that describe aspects of particle deposi-
tion. Saiers et al. [1994] modeled the transport and deposi-
tion of colloid anatase, boehmite, and silica in sand columns
by employing both first-order and second-order blocking
kinetic approaches. Abdel-Salam and Chrysikopoulos
[1994] presented an analytical solution for one-dimensional
colloid transport in a single rock fracture with and without
colloid penetration into the rock matrix.
[14] Johnson et al. [1996] incorporated both patchwise
geochemical heterogeneity and random sequential deposi-
tion dynamics in a one-dimensional colloid transport model.
Their model was used in one of the earliest trials where
heterogeneity was considered in colloid transport modeling.
They compared the model with the results from transport
experiments involving silica colloids traveling through a
column filled with geochemically heterogeneous sand
grains. Sun et al. [2001] developed a two-dimensional
colloid transport model for heterogeneous porous media
where they coupled the colloid transport equation with the
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
fluid – flow equation and used the finite element method to
obtain a numerical solution for these equations. Recently,
polydisperse (variable size) colloid transport in fractured sys-
tems has been investigated [James et al., 2005; Chrysikopoulos
and James, 2003; James and Chrysikopoulos, 1999, 2000].
These studies have shown that larger particles travel faster
than smaller particles and colloids with lognormal particle
size distribution encounter greater spreading than those with
uniform distribution.
[15] Many laboratory studies were conducted to under-
stand the interactions among contaminants, colloids, and
porous media. Laboratory experiments simulated colloids as
nonreactive substances by saturating the porous media with
colloids before beginning the experiments. The assumption
of nonreactive colloids was invoked by many authors
[Magee et al., 1991; Abdul et al., 1990; Dunnivant et al.,
1992]. As an example, the column experiments of Abdul et
al. [1990] focused on determining the washout efficiency
for a number of nonpolar organic contaminants. They found
that using a humic acid solution instead of water effectively
removes nonpolar organic contaminants. They attributed
this result to the effect of humic acid (colloids) on enhanc-
ing the migration of contaminants.
[16] Several models for contaminant transport in the
presence of colloids have been developed [e.g., Corapcioglu
and Jiang, 1993; Abdel-Salam and Chrysikopoulos, 1995a,
1995b; Corapcioglu and Choi, 1996; Roy and Dzombak,
1998; James and Chrysikopoulos, 1999, 2003; James et al.,
2005; Sun et al., 2001; Sen et al., 2004]. For example,
Corapcioglu and Jiang [1993] developed a one-dimensional,
homogeneous numerical model to describe colloid-
facilitated transport in saturated, nonfractured porous media
assuming linear equilibrium between the aqueous and solid
phase. They compared their model with the results of
column experiments. This model was the first attempt to
create a contaminant transport model in porous media in the
presence of colloids. Johnson et al. [1995] employed the
equilibrium model formulation to describe the results of
column experiments on enhanced transport of benzanthra-
cene by colloids. Roy and Dzombak [1998] studied the
effects of nonequilibrium sorption/desorption on colloid-
facilitated transport of hydrophobic organic compounds in
porous media. Magee et al. [1991] accounted for the
presence of colloids by developing a modified effective
retardation factor that could be used in the traditional
advection-dispersion transport equation.
[17] In a study of reactive solute transport in the presence
of dissolved organic carbon (DOC), Knabner et al. [1996]
and Totsche et al. [1996] showed the effect of DOC as a
contaminant-retarding agent. They reported anthracene
breaks through after 50 pore volumes in the absence of
DOC, whereas in the presence of DOC, breakthrough
occurred after 140 pore volumes. This experiment was
conducted under unsaturated flow conditions, and the
DOC comprised 34% mobile hydrophilic and 66% immo-
bile hydrophobic components.
[18] Sen et al. [2002] also considered the possibility that
colloids retard contaminant movement. Their results
showed increased retardation of Ni2+ under the plugging
condition. Bekhit and Hassan [2005a] and Bekhit et al.
[2006] examined numerically and experimentally, respec-
tively, the cases where colloids act as retardation agents and
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W08409
explored various conditions where colloids may retard the
transport of dissolved contaminants. In the context of
contaminant transport in rivers, Ren and Packman [2004,
2005] identified the retardation phenomenon, and they
termed it ‘‘colloid-impeded contaminant transport.’’
[19] As shown from the above discussion, an extensive
body of literature exists on colloid transport and colloid-
facilitated contaminant transport. However, the effect of
using different sorption isotherms (e.g., linear, Freundlich,
or Langmuir) in analyzing contaminant transport in the
presence of colloids has not been thoroughly addressed.
To the authors’ knowledge, only van de Weerd et al. [1998]
studied the effect of using the Langmuir isotherm in one-
dimensional, coupled transport of colloids and contami-
nants. They showed the effect of nonlinearity by comparing
results from using high initial concentration to results using
a lower initial concentration.
[20] The lack of these types of studies could be attributed
to the complexity of the problem, which makes the analyt-
ical solution of such problems extremely difficult. In addi-
tion, relying on the standard numerical approximation to
solve nonlinearity is not convenient for two reasons [van
der Zee, 1990]. The first reason involves constraints on the
time step and spatial discretization to overcome the insta-
bility problem. Secondly in some situations of nonlinear
transport, very sharp concentration gradients may develop
that require very fine discretization to obtain accurate
solutions.
[21] This study focuses on the effects of colloids on
transport of contaminants that sorb nonlinearly onto porous
media. We adapt the finite cell approach developed by Sun
[1999] to study the effect of nonlinear sorption on plume
transport. The main advantage of using the finite cell
approach for this problem is that it does not solve the
governing equations with the nonlinear terms. Instead, the
finite cell approach simulates advection and dispersion by
using the particle-tracking technique while sorption and
desorption (whether linear or nonlinear) are calculated
directly as mass exchange processes. Further, we examine
characteristics of the contaminant movement and distribu-
tion under linear and nonlinear sorption processes pertain-
ing to both contaminant and colloids.
[22] One of the important outcomes of this study is
providing a solution approach to the coupled partial differ-
ential equations describing colloid-associated contaminant
transport in porous media, for which a major strength has
not been realized in prior studies. Although the tool we use
here (the finite cell method) was developed and used in few
studies before [Sun, 1999, 2002] we highlight in this study
one of its major advantages. The method can handle
nonlinear reactions as easily as it can handle linear reac-
tions. We therefore capitalize on this strength and show how
this tool can be very useful in dealing with complicated
nonlinear, nonequilibrium contaminant reactions in the
presence of colloids.
[23] Another contribution in this study is the investigation
of the impact of colloids on a contaminant undergoing
nonlinear sorption. We also address in this study the cases
where both colloids and contaminant undergo nonlinear
deposition/sorption onto the solid matrix. To the best of
our knowledge, no prior study addressed this combined
nonlinearity. Again the realization of the full strength of
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
the finite cell approach was the key that allowed such
investigation.
[24] The study examines the impact on the plume shape
and illustrates the way in which sorption to aquifer mate-
rial and the presence of colloids can influence the overall
shape and migration rate of contaminant plumes. The study
provides new insights into the combined effects of con-
taminant concentration value, degree of nonlinearity, pres-
ence of colloids, and type of colloid deposition isotherm on
the plume migration rates and plume shape.
[25] A sensitivity of contaminant plume behavior to the
Freundlich isotherm exponent is presented. The results of
sensitivity analysis explained the effect of Freundlich iso-
therm exponent on plume travel distance, plume skewness,
and breakthrough curves. The effect of nonlinear isotherm
on the dilution of peak concentration is also investigated.
2. Model Description
[26] The movement of colloids and their interaction with
dissolved contaminants in groundwater systems are repre-
sented by six variables describing six constituents. The six
variables exist in the system and change in a dynamic
manner [Bekhit and Hassan 2005a, 2005b]. The first two
variables are the mobile colloid concentration and immobile
colloid concentration. The remaining four variables belong
to the contaminant and describe the different forms or states
that the contaminant can take in the system. These compo-
nents include (1) the mass concentration of contaminant
dissolved in the aqueous phase, (2) the mass concentration
of contaminant sorbing onto mobile colloidal surfaces,
(3) the mass concentration of contaminant sorbing onto
immobile colloidal surfaces, and (4) the mass concentration
of contaminant sorbing onto the solid matrix.
2.1. Colloid Transport Equations
[27] The mass balance equations for mobile and immo-
bile colloids are given by [Corapcioglu and Jiang, 1993]
@qCc
¼ r  J c  QSc ð1Þ
@t
@Sc
¼ QSc ð2Þ
@t
where Cc is the mass concentration of mobile colloids in the
aqueous phase (ML3); q is the porosity (dimensionless); Jc
is the specific mass flux of mobile colloids (ML2 T1),
which is the summation of flux due to advective flow,
mechanical dispersion, and Brownian diffusion; Qsc is the
net rate of colloid deposition on the solid matrix (ML3
T1), and Sc is the mass of captured (deposited or immobile)
colloids per unit total volume of porous media (ML3). The
specific mass flux Jc is given by
J c ¼ V qCc  ½DB þ DMD  rðqCc Þ ð3Þ
where DB is the Brownian diffusion coefficient (L2 T1);
DMD is the mechanical dispersion tensor of the colloids
(L2 T1); and V is the velocity vector (L T1). The term
@Sc
@t in equation (2) gives the mass exchange between
mobile colloids and solid matrix. This exchange can be
described by different reaction isotherms. A reaction
isotherm is determined in laboratory studies by
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W08409
comparing the sorbed concentration of colloids (or
contaminants) to the concentration of the same con-
stituent in solution at different levels for the latter
concentration value. Then this experimental data set is
fitted with an isotherm that may be linear or nonlinear.
That isotherm could either be considered in equilibrium
(very fast reactions compared to the transport char-
acteristic timescale) or in nonequilibrium (slow reac-
tions) conditions. The nonequilibrium case is more
general and is considered here. Thus the reaction of
colloids with the porous medium could be represented
in general by one of the following reaction equations:-
Linear kinetic isotherm:
1 @Sc K2
¼ K1 Cc  Sc ð4Þ
q @t q
Nonlinear kinetic Freundlich isotherm:
1 @Sc K2
¼ K1 CcNFrn  Sc ð5Þ
q @t q
Nonlinear kinetic Langmuir isotherm:


1 @Sc Smax  Sc K2
¼ K1 Cc  Sc ð6Þ
q @t Smax q
where K1 is the colloid deposition rate constant with
dimension (T 1 ) for equations (4) and (6) and
((ML3)1NFrn T1) for equation (5); K2 is the colloid
release rate constant (T1); NFrn is the exponent of the
nonlinear Freundlich isotherm; and Smax is the max-
imum amount of colloids that can be deposited onto the
solid matrix per unit volume of aquifer (ML3). Similar
isotherms can be written for contaminant interaction
with colloids (contaminant sorption onto and desorption
from colloids) and contaminant interaction with porous
medium (contaminant sorption-desorption processes).
[28] The linear kinetic isotherm accounts for a situation
where sorption is limited by a first-order kinetic model. The
linear isotherm is usually valid for dissolved species that are
present at concentrations less than one half of its solubility
[Lyman et al., 1992]. This isotherm was used to describe the
sorption of pesticides [Leistra and Dekkers, 1977; Hornsby
and Davidson, 1973] as well as some organics [Davidson
and Chang, 1972]. The Freundlich model is describing the
reversible nonlinear kinetic sorption, and it was successfully
used to describe the sorption of phosphate [Fiskell et al.,
1979] and herbicides [Enfield and Bledsoe, 1975]. The
nonlinearity of sorption is frequently correlated to the heat
of a sorption reaction [Weber and DiGiano, 1996]. Within
limited conditions, such as low solute concentration, the
nonlinearity of the Freundlich and Langmuir isotherms is
negligible so that the linear isotherm can be used without
substantial loss of accuracy [Papelis and Um, 2003].
2.2. Contaminant Transport Equations
[29] The mass balance equations for contaminant attached
to mobile and immobile colloids can be expressed as
[Corapcioglu and Jiang, 1993]
@
ðScm Cc Þ ¼ r  ½½DB þ DMD  rðqScm Cc Þ
@t
 r  ðV q Scm Cc Þ þ Q1  Q2 ð7Þ
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

1 @ tions [Kinzelbach, 1988; Valocchi and Quinodoz, 1989;

ðSc Scc Þ ¼ Q3 þ Q2 ð8Þ
q @t Tompson and Gelhar, 1990; LaBolle et al., 1996, 2000]


where Scm is the mass concentration of contaminant @Dxx @Dxy
sorbing onto mobile colloids per unit mass of colloids xtþDt ¼ xt þ Vx ðxt ; yt ; tÞ þ þ Dt
@x @y
(M/M); Scc is mass concentration of contaminant sorbing pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
onto immobile colloids per unit mass of colloids (M/M); þ 2Dxx Dt Z1 þ 2Dxy Dt Z2 ð11Þ
Q1 describes the mass exchange process between con-
taminant and mobile colloids (ML3 T1); Q2 accounts for 

the deposition and release of contaminant-carrying colloids @Dyx @Dyy
ytþDt ¼ yt þ Vy ðxt ; yt ; tÞ þ þ Dt
onto and from solid matrix (ML3 T1), and Q3 describes pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
@x
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
@y
the interaction between contaminant and immobile colloids þ 2Dyx Dt Z1 þ 2Dyy Dt Z2 ð12Þ
(ML3 T1). Lastly, the mass balance equations for
dissolved contaminant and for contaminant sorbing where x and y are the coordinates of the particle location
directly onto the solid matrix are given by (L); Vx and Vy are the velocity components in the x and y
directions (L T1), respectively; Dij is the ij component of
@     the dispersion tensor (summation of Brownian diffusion and
qCf ¼ r  ½DB þ DMD  rq Cf
@t   mechanical dispersion), Dt is the time step (T); and Z is a
 r  V q Cf  Q1  Q3  Q4 ð9Þ normally distributed random number having zero mean and
unit variance. The second term multiplied by Dt on the right
hand side of equation (11) is an effective velocity that
@Ss combines local velocity at location (xt, yt) and time t plus the
¼ Q4 ð10Þ
@t gradient of the dispersion tensor at location (xt, yt). The last
two terms account for the local-scale dispersion and
where Cf is the mass concentration of contaminant Brownian diffusion. Since we are dealing with homogenous
dissolved in the aqueous phase (contaminant mass per conditions, the terms involving the gradient of the
unit aqueous volume) (ML3); Ss is the mass concentra- dispersion coefficients are dropped from equations (11)
tion of contaminant sorbing onto the solid matrix per unit and (12). Only advective and local-scale dispersion terms
total volume of porous media (ML3); and Q4 accounts are used in this study.
for the sorption process between the contaminant and the [32] Mass exchange occurs between dissolved contami-
solid matrix (ML3 T1). Note that the terms Q1, Q2, Q3, nant and mobile colloids carried in the same cell or when a
and Q4 can be represented using kinetic interactions mobile cell containing contaminant or colloids crosses an
similar to those given in equations (4), (5), and (6). The immobile cell during transport. This exchange is controlled
details of how these interactions are implemented in the by the kinetic interaction and sorption isotherms, which are
finite cell method are presented in the next section. given in equations (4) – (6). For example, consider that a
contaminated mobile cell interacts with the solid matrix
3. Numerical Solution according to the nonlinear Freundlich isotherm given by
equation (5). This mass exchange can be expressed as
3.1. Finite Cell Method
[30] A common numerical approach for solving trans-  
Ss
port problems including reactive transport is the particle- DmCf ¼ Kf CfNFrn  Kb
Vw Dtr ð13Þ
q
tracking method [e.g., Tompson and Gelhar, 1990; Bellin
et al., 1992; Chin and Wang, 1992; Hassan et al., 1997, where DmCf is the mass change in the mobile cell (M); Vw is
1998, 2001]. Particles representing the contaminant plume the volume of water in the mobile cell (L3); Kf is the
are displaced in space over discrete time steps by the action forward rate constant with dimension [(ML3)1NFrn T1];
of some driving mechanisms such as a chemical potential or Kb is the backward rate constant [T1]; and Dtr is the time
a velocity field. The finite cell method, developed by Sun of interaction between the mobile and immobile cells (T),
[1999], is a variation of the particle tracking concept where which is a fraction of the time step, Dt. After calculating the
particle mass is distributed over a volume (a finite cell) change in mass, both the mobile and immobile concentra-
rather than at a point. This method represents the different tions are updated as
phases in a certain problem with different sets of cells; each
cell is assigned mass, concentration, and volume fractions MCf  DmCf
of the particular constituent. Interactions among these cells Cf ¼ ð14Þ
Vw
and exchanges in mass can then be carried out in a manner
consistent with the phenomenological understanding of the
involved processes. More details about the finite cell
MSs þ DmCf
method can be found in work by Sun [1999, 2002]. Ss ¼ ð15Þ
Vw =q
3.2. Numerical Implementation
[31] The solution of the differential equation governing where MCf is the mass of contaminant in the mobile cell at
the movement of mobile cells can be approximated by the beginning of the time step (M) and MSs is the sorbed
tracking cell movement in time and space. Tracking in two
dimensions is based on the standard random walk equa-
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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Table 1. Parameter Values for the Test Case Comparing the Finite
Cell Solution to the TVD Finite Difference Solution @C @C  
ðx; 0; t Þ ¼ x; Wy ; t ¼ 0 ð19Þ
Description Parameter Value @y @y

Initial mobile colloid concentration Cc0 100 g m3 where C represents any of the three mobile concentrations
Initial dissolved contaminant Cf0 100 g m3
concentration (Cc, Cf, and Scm); C0 is the initial concentration; Lx is the
Initial concentrations Sc0 = Scm0 = Scc0 = S0 0.0 g m3 domain length in the x direction; and Wy is the domain width
Porosity q 0.3 in the y direction.
Velocity in x direction Vx 0.5 m d1 [37] The two models (finite cell and finite difference) are
Velocity in y direction Vy 0.0 m d1 used to simulate an instantaneous pulse of contaminant
Longitudinal dispersivity aL 0.1 m
Transversal dispersivity aT 0.05 m
released into the simulation domain at time t = 0. A colloid
Colloid release rate K2 0.5 d1 plume is assumed to coincide with the dissolved con-
Contaminant desorption rate Kb 0.5 d1 taminant plume as an initial condition. All interactions are
Contaminant sorption rate Kf 1 d1 assumed to follow a linear isotherm. Therefore the terms Q1,
Reaction rate coefficients (colloid K1 = Ksm = Ksc 1 d1 Q2, Q3, and Q4 are given by
deposition rate and contaminant
desorption rate)
Rates of contaminant sorption Kam = Kaim 3 d1 Q1 ¼ Kam Cf  Ksm Scm Cc ð20Þ
onto colloids

K2
Q2 ¼ K1 Scm Cc  Sc Scc ð21Þ
q
contaminant mass in the immobile cell at the beginning of
the time step (M). Note that if DmCf is positive, the
Ksc
dissolved contaminant concentration, Cf, decreases at the Q3 ¼ Kaim Cf  Scc Sc ð22Þ
end of the time step, whereas the sorbed concentration, Ss, q
increases. The opposite is true if DmCf is negative.
Kb
Q4 ¼ Kf Cf  Ss ð23Þ
4. Model Verification and Test Problem q

[33] In order to test the accuracy of the finite cell solution
for contaminant transport in the presence of colloids, we
compare the finite cell results to the TVD, finite difference
solution presented by Bekhit and Hassan [2005a]. The finite
difference model was previously verified using mass
balance tests and was compared to analytical solutions
and experimental data [Bekhit and Hassan, 2005a, 2005b].
[34] A two-dimensional domain of size 52
26 m2 is this test case are similar to those used by Corapcioglu and
considered. The domain is divided into a uniform grid of
square blocks of length Dx = Dy = 0.2 m, which gives a
total of 32,768 blocks (128 rows
256 columns). Each grid [38] Figures 1a and 1b compare the spatial distribution of
block is divided into 16 immobile cells, and the water
contained within each grid block is divided into 16 mobile
cells having equal volume. This gives a total of 524,288
mobile cells.
[35] Two types of boundary conditions are employed
throughout the model domain: (1) no-flow boundaries along
the base and top of the model domain and (2) constant head
boundaries along the left and right edges of the model
domain. These conditions result in a unidirectional flow
(from left to right with a uniform velocity of 0.5 m d1).
Having homogeneous conditions, no vertical velocity com-
ponents exist in the domain.
[36] The following initial and boundary conditions are
employed for the transport problem
C ðx; y; 0Þ ¼ C0
C ð0; y; tÞ ¼ 0
where Km im
a and Ka are the sorption rate coefficients of
contaminant on mobile and immobile colloids, respectively,
[T1]; Ksm is the desorption rate coefficient of contaminant
from the mobile colloids [T1]; and Ksc is the desorption
rate coefficient of contaminant from the immobile colloids
[T1]. The values of rate coefficients and initial conditions
are summarized in Table 1. The values of the parameters for
Jiang [1993], Roy and Dzombak [1998], Corapcioglu and
Wang [1999], and Kim and Corapcioglu [2002].
the mobile and immobile colloid plumes at t = 40 days
using the finite difference method (solid line) and finite cell
method (dashed line). In Figures 1c –1f, the four con-
taminant constituents (Scm, Scc, Cf, and Ss) are compared
using finite difference and finite cell methods. As can be
seen from Figure 1, a very good match between the two
models is obtained for the six plumes. This agreement
indicates that the numerical solution for the finite cell model
successfully represents colloid transport and associated
contaminant transport. It is important to note that the
agreement is very good for all six constituents. Presenting
these six plumes guarantees the good performance of the
solution better than if one only compares total mobile
contaminant concentration (i.e., Cf + ScmCc). There are
minor oscillations in the finite cell solution, which result
ð16Þ from the discrete nature of the cells and random component
of their movement. Such oscillations can easily be
smoothed out by increasing the number of mobile cells
ð17Þ per grid block.

@C
5. Results and Discussion
ðLx ; y; tÞ ¼ 0 ð18Þ [39] Discussion of the analyses and results is divided into
@x
four main parts or subsections. First, the effect of kinetic
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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 1. Comparison between the finite cell solution (solid contours) and the finite difference solution
(dashed contours) for colloid and contaminant transport in a two-dimensional domain 40 days after plume
release.

nonlinear Freundlich isotherm is investigated for contami-
nant migration in a homogenous porous medium. This
effect is studied under two levels of nonlinearity, NFrn =
0.5 and NFrn = 1.3, in the presence and absence of colloids.
Because of the nature of nonlinear isotherms, the magnitude of
retardation depends on the values of both NFrn and the
concentration. To explore these effects and investigate the
influence of colloids, the analysis is performed with initial
concentration of 1.0 g m3, and the results are compared to
solutions with an initial concentration much larger than
1.0 g m3. Second, the impact of nonlinearity in contaminant
sorption on plume dispersion and skewness is investigated in
the presence and absence of colloids. The same cases used in the
first part are used to study plume shape.
[40] Third, the impact of limited colloidal sorption
capacity on the contaminant transport is studied. In this
analysis, the colloids are assumed to have a limited sorption
capacity, and the sorption of contaminant onto colloids is
represented by the Langmuir isotherm. A reference case is
first established where colloids are assumed to have unlim-
ited sites (contaminant sorption onto colloids is assumed to
follow a linear kinetic isotherm). The amount of contami-
nant that sorbs onto colloids in the reference case is
computed and denoted as Sref. Four cases are then presented
where the maximum capacity for colloids to hold the
contaminant is assumed to be 75%, 50%, 25%, and 10% of
Sref. Comparisons among these cases and with the reference
case are presented.
[41] Fourth, the role of colloids to enhance contaminant
transport is evaluated when colloid deposition onto solid
matrix is nonlinear. To study this aspect, two scenarios are
examined. In the first scenario the Freundlich isotherm is
used for colloid deposition, whereas the second scenario
assumes colloids to have a linear sorption isotherm. In the

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Figure 2. Cumulative mass arrival curves (left axis, solid line) and maximum concentration (right axis,
dashed line) of the dissolved contaminant Cf (a) in the absence of colloids and (b) in the presence of
colloids for Cf0 = 100 g m3.

two scenarios, contaminant sorption onto colloids is as-
sumed to follow the Langmuir isotherm.
[42] The same two-dimensional domain and flow con-
ditions described in section 4 are used here. For the
transport problem, an instantaneous contaminant is released
into the simulation domain at time t = 0 with an initial size
of 1
3 m. A colloid plume is assumed to coincide with the
dissolved contaminant plume at t = 0. In addition, we assign
a control plane (5 m away from the source) normal to the
flow direction. The cumulative mass arrival across the
control plane and the maximum concentration at the control
plane are obtained as a function of time. The model
parameters have been selected on the basis of literature
values. Unless stated otherwise the following reaction rates
are used: K1 = 1 d1, K2 = 0.5 d1, Km 1 im 1
a = 2 d , Ka = 2 d ,
Ksm = 0.5 d1, Ksc = 4 d1, Kf = 1 d1, and Kb = 0.5 d1. In
addition, the physical properties remain constant in all
simulations where q = 0.3; Dxx = Dyy = 0.025 m2 d1; and
total simulation time is 80 days. The term ‘‘total
contaminant concentration’’ is used to denote the summa-
tion of dissolved contaminant concentration and concen-
tration of contaminant sorbed onto mobile colloids (i.e.,
CTotal = Cf + ScmCc).
5.1. Effect of Nonlinear Freundlich Isotherm
on Contaminant Retardation
[43] We consider an aquifer contaminated with an instan-
taneous spill with Cf0 = 100.0 g m3 and assume that the
contaminant sorbs onto solid matrix nonlinearly according
to a Freundlich isotherm. Two cases are simulated where
NFrn = 0.5 in the first case and NFrn = 1.3 in the second case.
In both cases, Kf is taken as 0.5 (g m3)NFrn d1. Figure 2a
gives the cumulative mass arrival across the control plane
(left axis—solid lines) and the maximum concentration at
the control plane (right axis—dashed line) for the two cases
in the absence of colloids. Figure 2a shows that an early
arrival of the plume in the case of NFrn =0.5 is obtained with
a peak concentration that is about 390% higher than the case
of NFrn = 1.3. The plume experiences greater retardation in
the case of NFrn = 1.3. These results are in agreement with the

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 3. Cumulative mass arrival curves (left axis, solid line) and maximum concentration (right axis,
dashed line) of the dissolved contaminant Cf (a) in the absence of colloids and (b) in the presence of
colloids for Cf0 = 1 g m3.

analytical traveling wave solution for nonlinear nonequili-
brium contaminant transport developed by van der Zee
[1990].
[44] Figure 2b is similar to Figure 2a, but the contaminant
transport results are obtained in the presence of colloids. A
colloid plume having Cc0 = 100 g m3 is released and is
assumed to coincide with the contaminant plume. However,
to investigate the effect of nonlinear reactions separately, the
isotherm governing colloid deposition onto the solid matrix
is assumed to be linear. It is important to note that the initial
colloid concentration value selected for these simulations is
consistent with field findings regarding colloid concentra-
tion in soils. Results from field studies have demonstrated
that soil colloids may be released to drainage water in high
concentrations during rainfall events [Ryan et al., 1998;
El-Farhan et al., 2000; Villholth et al., 2000; Petersen et al.,
2003]. Also, data collected from the field at the Nevada Test
Sites [Kersting et al., 2003] show that ‘‘. . .colloids were
found in every sample, although there was a large variation
in concentration (0.0002 – 200 mg L1).’’ Concentrations in
excess of 1 g L1 (1000 g m3) have been reported during
simulated and natural rainfall events [DeNovio et al., 2004,
Table 1].
[45] It is evident from Figure 2b that the presence of
colloids facilitates transport of the contaminant for the case
of NFrn = 1.3. The 50% mass arrival time for contaminant
(Figure 2a) is 26 days in the absence of colloids and 16 days
in the presence of colloids. On the other hand, when NFrn =
0.5, the presence of colloids retards the contaminant
transport (e.g., the 50% mass arrival time increased from
10 to 12 days because of the presence of colloids). The
combined effects of nonlinear isotherm and the presence of
colloids are discussed at the end of this section.
[46] Bekhit [2004] found that the effective retardation of a
contaminant plume experiencing nonlinear reaction is
highly dependent on the initial concentration. To examine
this phenomenon in the presence of colloids, the previous
analysis is repeated under small initial concentration.
Figure 3 is thus similar to Figure 2, but is based on using
a value for Cf0 of 1 g m3. It is shown in Figure 3a that the

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
Figure 4. Schematic diagram showing the combined effect of colloids and nonlinear contaminant
sorption on the contaminant transport.
plume experiences greater retardation in the case of NFrn =
0.5 than in the case of NFrn = 1.3. Fifty percent of the initial
mass crossed the control plan after 14.5 days when NFrn =
1.3, whereas only 40% of the initial mass crossed the
control plan after 80 days when NFrn = 0.5. Comparing
Figures 2a and 3a indicates that the impact of NFrn is altered
on the basis of the value of the dissolved contaminant
concentration. These results are in agreement with the
sorption of organic component data reported by Appelo and
Postma [1993] who state that the distribution coefficients
for many organic compounds are smaller for high than for
low concentration. These results are attributed to the fact
that the sorption capacity decreases when the concentration
increases, provided that 0 < NFrn < 1.
[47] As can be seen from the two cases examined in
Figure 3, colloids enhance contaminant transport in both
cases. However, colloids effect is more pronounced when
NFrn = 0.5, where colloids significantly reduce the 50%
mass arrival time from more than 80 days in the absence of
colloids to only 37 days in the presence of colloids. Also,
the peak concentration at the control plane has a value of
about 0.04 g m3 and occurs at 30 days in the absence of
colloids, whereas it increases to 0.06 g m3 and occurs at
W08409
colloids is less than in the absence of colloids. This is
because colloids uphold some of the contaminant mass on
its surfaces thereby reducing the amount of contaminant
sorbing directly onto the solid matrix.
[49] Because of the nature of the nonlinear isotherm and
under certain conditions (i.e., contaminant concentration,
Freundlich exponent, and colloids and contaminant interac-
tion with the solid matrix), colloids could retard the con-
taminant. Figure 4 shows a schematic diagram that explains
the role of colloids in facilitating or retarding the contam-
inant transport. The top line in Figure 4 shows cases of
nonlinear sorption resulting in highly retarded contaminant
plume (left), mildly retarded plume (middle), or low-
retardation plume (right). The effective velocity line shows
the relative position of the plume in the three cases. These
cases depend on the combination of Cf and NFrn as shown
in Figure 4. The middle line in Figure 4 displays a
hypothetical location of a colloid plume. When the
contaminant and the colloids are put together (bottom line),
either colloid-facilitated or colloid-retarded transport is
obtained.
[50] Therefore, if a contaminant transport is controlled by
nonlinear isotherm with a relatively high retardation factor
22 days when colloids are present. It should be noticed that
colloids did not significantly enhance the 50% mass arrival
time of the contaminant for the case of NFrn = 1.3. However,
colloids increased the maximum concentration crossing the
control plane by about 37.5%. Therefore one could claim
that colloids enhance the contaminant transport in both
cases presented in Figure 3.
[48] In the presence of colloids, the total sorption of
contaminant consists of two components. The first is the
direct sorption of contaminant onto solid matrix, and the
second is the indirect sorption of contaminant (i.e., contam-
inant sorbed onto colloids that are deposited onto the solid
matrix). However, in the absence of colloids, only direct
sorption exists. The amount of total sorption controls how
fast the contaminant migrates and determines the effective
retardation factor. Generally, the amount of contaminant
directly sorbing onto the solid matrix in the presence of
10 of 19
(e.g., Cf  1 and NFrn > 1 or Cf  1 and NFrn < 1), the
presence of colloids facilitates the contaminant transport.
On the other hand, if the contaminant plume experiences
nonlinear isotherm resulting in a small retardation factor, the
presence of colloids may facilitate or retard the contaminant
transport. For example, under the conditions described in
Figure 2b (i.e., Cf0 = 100 g m3, Cf  1.0 g m3 and Nfrn < 1),
colloids retard the contaminant transport.
[51] The results in Figures 2a and 3a indicate that for a
contaminant plume undergoing nonlinear sorption and with
a certain initial concentration value, the plume is either
strongly retarded or mildly retarded (compared to conser-
vative transport) depending on the value of NFrn. For Cf0 =
100 g m3, nonlinear sorption with NFrn > 1.0 yields
stronger retardation than with NFrn values smaller than 1.0
(compare the mass arrival curves in Figure 2a to the 50%
arrival time of a conservative contaminant shown in
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 5. Contour map showing the zones where colloids facilitate contaminant transport (solid
contours) and the zones where colloids retardate transport (dashed contours).

Figure 2a). Similarly, for Cf0 < 1.0, nonlinear sorption with
NFrn values smaller than 1.0 yields stronger retardation than
with NFrn values larger than 1.0.
[52] When the contaminant experiences mild to little
retardation (Figure 4), a large portion of the dissolved plume
(Cf) travels with small retardation, and only the plume tail
migrates with a large effective retardation factor. Moreover,
the contaminant carried by colloids (Scm) moves with a
uniform effective retardation factor (because of the linear
isotherm used for colloid deposition) that is less than the
retardation factor of the slowest part of the Cf plume but
larger than the retardation factor of the fastest part. Thus the
presence of colloids facilitates part of the plume and retards
another part, and therefore, depending on the ratio between
the fastest and slowest portions of the Cf plume, the overall
effect of colloids could be one of retardation (Figure 2b,
NFrn = 0.5) or facilitation (Figure 2b, NFrn = 1.3) of the total
contaminant transport.
[53] An important aspect here is to quantify the cases
under which colloids may facilitate or retard contaminant
transport. To address this aspect, a contour map is created in
the parameter space which shows the ratio of the plume-first
moment (a measure for the travel distance of the center of
mass) in the presence and absence of colloids after 80 days
under different Freundlich exponent and initial concentration
values (Figure 5). In Figure 5, y axis gives the natural
logarithm of the initial concentration ranging from
[0.1 g m3 to 1000 g m3], x axis gives the Freundlich
exponent, and the contour values give the ratio of the first
moment in the presence of colloids to the first moment in
the absence of colloids (X1j with colloids/X1j without colloids). As
shown in Figure 5, under the examined conditions, there are
clear zones where colloids may facilitate or retard the
transport of a contaminant experiencing nonlinear sorption.
The threshold values (dashed thick lines) are located around
a Freundlich exponent of value equal to 1, and an initial
concentration around 31 g m3. It is expected that the
threshold of NFrn = 1 will remain the same under conditions
different than what we used in Figure 5. However, the initial
concentration will vary on the basis of the different reaction
rates.
5.2. Effect of Nonlinear Freundlich Isotherm
on the Plume Shape
[54] To examine the effect of nonlinear sorption on the
shape of the contaminant plume, a snapshot of the contam-
inant plume is plotted. Figure 6 shows the distribution of a
plume resulting from an instantaneous initial source of Cf0 =
100 g m3 80 days after the plume was released. Plume
distributions presented in Figure 6 reveal interesting
findings. The contaminant plume exhibits positive skewness
at NFrn = 1.3 and negative skewness at NFrn = 0.5, both in
the presence and absence of colloids. This could be
attributed to the nature of the nonlinear isotherm. As
discussed previously, with the initial concentration Cf0 =
100 g m3, the higher-concentration area travels faster than
the lower-concentration area when NFrn < 1.0. Therefore
most of the mass of the contaminant plume travels faster

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 6. Comparison between plume distributions in the presence and absence of colloids at t = 80 days
under different NFM values with Cf0 = 100 g m3.

and causes a negative skewness. The opposite trend occurs
when NFrn > 1.0, where most of the mass of the plume
(having the higher-concentration values) is highly retarded,
and the lower-concentration areas in the plume front travel
with much less retardation resulting in the positive
skewness of the plume.
[55] The results also indicate that colloids reduce skew-
ness in the plume. Under nonlinear sorption, the higher and
lower concentrations exhibit differing effective retardation
factors with the value of the Freundlich exponent and
concentration determining which portion moves faster.
However, the presence of colloids facilitates mobility of
the slower portion of the plume and slightly decreases or
does not affect (on the basis of the degree of nonlinearity)
the mobility of the faster portion of the plume. As a result,
the entire plume migrates with more or less the same level
of retardation, and therefore the skewness of the plume is
reduced in the presence of colloids.
[56] To gain a better understanding of colloids effects
when Cf < 1, the same conditions used in Figure 6 are
used in Figure 7 except Cf0 is changed to 1 g m3. Figure 7
displays the plume distribution after 80 days of plume
release with and without colloids under the same two levels
of nonlinearity. The same trend is obtained as in the case of
Cf0 > 1, where the contaminant plume exhibits positive
skewness at NFrn = 1.3 and negative skewness at NFrn = 0.5

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 7. Comparison between plume distributions in the presence and absence of colloids at t =
80 days under different NFrn values with Cf0 = 1 g m3.

with the presence of colloids not impacting the plume
skewness in the first case (Figure 7b) and reducing
skewness of the plume in the second case (Figure 7d).
[57] Another observation from Figures 6 and 7 indicates
the presence of colloids affects dispersion of the plume.
When the sorption impact is small (i.e., Cf > 1.0 and NFrn <
1.0 or Cf < 1.0 and NFrn > 1.0), colloids reduce dispersion of
the plume. However, when the sorption effect is significant
(i.e., Cf > 1.0 and NFrn > 1.0 or Cf < 1.0 and Nfrn < 1.0),
colloids increase plume dispersion. When the sorption effect
is small, part of the plume does not sorb onto the solid
matrix and does not experience retardation. In this case, the
presence of colloids reduces dispersion, because on one
hand it provides more sorption sites and slows down the
faster portion of the plume, and on the other hand it
facilitates the mobility of the slower portion of the plume.
However, when the sorption impact is significant, the plume
also experiences different retardation factors that correspond
to the concentration, but these retardation factors are so
large that the plume is somewhat trapped and does not
migrate a significant distance. Accordingly, the plume
dispersion is small in these conditions. The presence of
colloids under these conditions provides a carrier for the
contaminant that facilitates transport of the plume and
therefore increases the dispersion due to a longer traveling
distance.
[58] It is also of interest to note that in all previous results,
the presence of colloids reduces the difference among the
results (e.g., mass flux breakthrough, arrival time, concen-
tration, and plume dispersion) of the two nonlinear Freund-
lich exponent values. This aspect of the results implies that
if uncertainty exists in the value of the Freundlich exponent,
the presence of colloids reduces uncertainty in the results.
This finding is consistent with the results presented by
Bekhit and Hassan [2005b] which show reduction in the
uncertainty range in the contaminant arrival times in a

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 8. (a) Cumulative mass arrival curves and (b) maximum concentration of the total mobile
contaminant (CTotal = Cf + ScmCc) at the control plane in the presence of colloids with different sorption
capacity.

heterogeneous flow field caused by the presence of colloids.
To the best of our knowledge, this has not been recognized
in previous colloid-contaminant studies.
5.3. Effect of the Langmuir Isotherm
[59] Here, the effect of limited capacity of colloidal
surfaces to hold contaminant is the focus. As described
previously, a reference case is established where colloids are
assumed to have unlimited sorption sites. This case relies on
a linear kinetic isotherm to predict the sorption of contam-
inant onto colloids. The mass of contaminant attached to
mobile colloids per unit mass of mobile colloids in the
reference case is found to be 87% whereas for the immobile
colloids this ratio is 23%. Therefore the attachment capacity
of the reference case (Sref) is assumed to be 55%, which is
the average mobile and immobile colloid capacities.
Although this assumption cannot be grounded by data, the
results will reveal the effect of the colloid-limited sorption
capacity in a relative sense regardless of the value of Sref.
[60] Four cases similar to the reference case are simulated
but with the assumption that contaminant sorption onto
colloids follows a Langmuir isotherm with a maximum
sorption capacity of 41.25%, 27.5%, 13.75%, and 5.5%,
which represent 0.75 Sref, 0.5 Sref, 0.25 Sref, and 0.1 Sref,
respectively. Figure 8 summarizes the comparison among
these cases, where Figure 8a shows the cumulative mass
arrival and Figure 8b displays maximum concentration at
the control plane as a function of time.
[61] Implementing limited sorption capacity through the
Langmuir isotherm significantly reduces the colloids effect.
It is evident from the results that, under linear sorption
(unlimited sorption capacity), colloids decrease the 50%
mass arrival time by approximately 31%, whereas under
limited sorption capacity of 0.75 Sref and 0.25 Sref, colloids
facilitate transport by only 11% and 3%, respectively.
Moreover, results show that overestimates of peak con-
taminant concentration occur when the effect of limited
colloidal sorption sites are not considered. It should be
mentioned that assuming linear sorption is not always a
conservative assumption. As discussed by Bekhit and
Hassan [2005a] and shown in Figure 4, colloids may retard
the contaminant, and in this situation, the presence of
colloids and the use of the linear sorption assumption are
not necessarily a conservative assumption.
[62] Different colloid-contaminant initial concentrations
with the Langmuir isotherm are compared to the linear
sorption case and also to the colloid-free case. Four Cc0/Cf0
ratios of 0.1, 1, 10, and 100 are used, and the maximum
sorption capacity is fixed at 0.5 Sref. Figure 9 summarizes
these simulations. Results show that when the colloid
concentration is low as compared to contaminant concen-
tration, the effect of colloid on transport is minor and can be
neglected, as the results of this simulation are very similar to
the colloid-free case. On the other hand if colloids exist in a
large concentration compared to the contaminant concentra-
tion, the results predicted from a Langmuir isotherm are the
same as predicted from the linear sorption isotherm.
Therefore, above a certain ratio Cc0/Cf0 (e.g., Cc0/Cf0 > 100
in the examined scenarios) and depending on the other
parameters, one could assume that colloids have unlimited
sorption sites and use a linear isotherm without losing
accuracy in the solution.
5.4. Effect of Coupled Freundlich
and Langmuir Isotherms
[63] Here we present a scenario combining nonlinear
colloid deposition with the assumption that colloids have
limited sorption sites. This scenario implies that the attach-

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W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

Figure 9. Effect of colloid-contaminant initial concentration ratio on the total mobile contaminant
breakthrough assuming contaminant sorption onto colloids to follow a Langmuir isotherm with Smax =
27.5%.

ment of contaminant to colloids follows a Langmuir iso-
therm. Three scenarios are compared where the first two
scenarios represent colloids that are deposited onto the solid
matrix with a nonlinear Freundlich isotherm with NFrn = 0.5
or NFrn = 1.3. The third scenario represents colloids
deposition with a linear sorption isotherm. In these three
scenarios, contaminant sorption onto colloids is assumed to
follow a Langmuir isotherm with maximum capacity of
0.75 Sref. Initial colloid concentration is taken as 100 g m3
and initial contaminant concentration is taken as 100 g m3.
[64] As shown in Figure 10, when NFrn = 0.5 for the
colloid deposition, it results in early arrival of the
contaminant breakthrough as compared to the case when
NFrn = 1.0 (linear isotherm). However, this early arrival
occurs until 20% of the contaminant mass crosses the
control plane, then the contaminant breakthrough exhibits
greater retardation than in the linear sorption case. For the
case of NFrn = 1.3, the entire breakthrough is more retarded
than in the case of linear colloid sorption.

Figure 10. Cumulative mass arrival curves of total mobile contaminant in the presence of colloids
under different NFrn values for the colloid deposition isotherm.
15 of 19
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
[65] In the case of the linear deposition isotherm, the
entire colloid plume moves with uniform retardation factor,
RLin, whereas in the case of a nonlinear isotherm, the plume
travels with different retardation on the basis of the
concentration value. When NFrn = 0.5 and Cc0 = 100 g m3,
the high colloid concentration zone travels with an effective
retardation factor smaller than RLin, and the small-
concentration zone travels with a retardation factor greater
than RLin. Therefore the faster portion of the colloids plume
carries part of the contaminant and causes early arrival. At
the same time, the slower portion of the colloids plume
holds the contaminant in the immobile phase and causes
retardation in the rest of the breakthrough. When NFrn = 1.3
and because the colloid concentration is much larger than
1.0, all retardation factors of the colloids plume are larger
than RLin.
[66] The results also show that the contaminant break-
through with NFrn = 0.5 is faster than in the case of NFrn =
1.3 until about 70% of the mass crosses the control plane;
then the situation is reversed. At early times, the colloid
concentration value is still high and the retardation for the
case of NFrn = 0.5 is much less than in the case of NFrn =
1.3. With the colloids plume’s advection-dispersion, and
reaction (deposition and release) colloid concentration is
diluted and the retardation factor for the case of NFrn = 0.5
increases, whereas the retardation factor for the case of
NFrn = 1.3 decreases. Consequently, at late times, the two
breakthrough curves change position.
[67] This analysis indicates that assuming colloid depo-
sition onto solid matrix to follow a linear isotherm is a
conservative assumption if the peak concentration is the
quantity of interest. Figure 10 shows that the 50% mass
arrival time under a linear isotherm is earlier than in the other
two cases where NFrn = 0.5, and 1.3. However, the linear
isotherm is not a conservative assumption if the contami-
nant of interest could cause a serious environmental
problem, even if at low concentration levels. In that case,
assuming nonlinear colloid deposition may provide a more
conservative estimate of the earliest arrival time than
provided with a linear isotherm when colloids are abundant
in the system.
6. Summary and Conclusions
[68] In this study, the effect of colloids on contaminant
transport under nonlinear nonequilibrium sorption is inves-
tigated. Linear sorption, Freundlich sorption, and Langmuir
sorption isotherms are considered. The finite cell method,
originally developed by Sun [1999], is adapted and
extended to solve the colloid-contaminant transport problem
under nonlinear reactions. The finite cell method is based on
the common particle-tracking technique that overcomes the
complexity involved in solving the nonlinear transport
equations.
[69] The results presented in this paper reveal that con-
taminant plumes do not experience uniform retardation
under the Freundlich sorption isotherm. The nonlinear
sorption dramatically affects the contaminant transport.
Therefore, if data show a nonlinear trend for contaminant
sorption onto solid matrix, ignoring the nonlinear sorption
and simplifying it by a linear process may provide mislead-
ing results.
16 of 19
W08409
[70] We highlight the effect of the values of concentra-
tions (low versus high) on the contaminant plume retarda-
tion under nonlinear sorption and the interplay with the
value of the nonlinear isotherm exponent. When colloids are
present their impact on plume movement is dependent upon
the values of the contaminant concentration and the non-
linear sorption exponent. This means that for the same
situation in the field and as the plume migrates, disperses,
and attenuates, the colloids impact on the plume at early
times (when concentrations are still high) can be different
than at later times when concentrations become small. The
colloids impact may change from a status of contaminant
movement facilitation to that of movement retardation or
vice versa depending on the degree of nonlinearity of the
contaminant reaction.
[71] The interplay between concentration values and the
degree of nonlinearity as shown in the results of this study
has important implications in modeling high-level radioac-
tive waste disposal sites (e.g., nuclear testing sites). At these
sites, initial concentrations are sometimes considered clas-
sified information, and modeling relies on an initial unit
mass or concentration for any radionuclide of interest [Pohll
et al., 1999; Hassan et al., 2001; Pohlmann et al., 2000,
2002]. In such cases, nonlinear reactions cannot be
considered as they require the knowledge of the actual
initial concentration value, and the modeling results based
on initial unit concentration are not linearly scalable if the
contaminant undergoes nonlinear reactions. The presence of
colloids adds more complexity in the sense that it is not
readily known which scenario becomes more conservative
(i.e., providing higher safety factor). A conservative
assumption indicates an assumption that provides more
safeguard against underestimating contaminant migration
rates or travel distances.
[72] We also show that colloids impact on the contami-
nant migration may be altered from facilitating the move-
ment to retarding it depending on the contaminant
concentration values and the degree of nonlinearity of the
reaction. The phenomenon that colloids may act as retarding
agents has only been recognized in few recent studies in the
literature [Knabner et al., 1996; Totsche et al., 1996; Sen et
al., 2002; Ren and Packman, 2004, 2005; Bekhit and
Hassan, 2005a; Bekhit et al., 2006]. However, we quantify
the cases and determine parameter combinations under
which the colloids act as facilitating or retarding agents to
contaminants experiencing nonlinear reactions. Threshold
values of the contaminant concentration and the nonlinear
Freundlich exponent are devised to delineate areas on the
parameter space where colloids facilitate or retard the
contaminant movement.
[73] Assuming that colloids have unlimited sorption sites
could also produce inaccurate and misleading results. To
account for limited sorption sites on colloidal surfaces,
contaminant sorption onto colloids can be assumed to
follow a Langmuir isotherm. The results show that to better
predict the potential for colloid-facilitated transport, the
actual colloid concentration and estimated colloid sorption
capacity should be carefully characterized.
[74] For colloid-facilitated or colloid-retarded contami-
nant transport in natural porous media, the modeling results
presented here indicate that high-concentration contami-
nants that sorb strongly nonlinearly to the aquifer material
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
can be carried further from the source of contamination. The
contrasting transport results of low- and high-concentration
plumes, and the two levels of nonlinearity (NFrn < 1 and
NFrn > 1) presented in this study emphasize the need to
evaluate contaminant sorption kinetics and degree of
sorption nonlinearity for a better assessment of colloid-
associated transport.
[75] Finally, the choice of linear versus nonlinear iso-
therms for colloid deposition and the resulting influence on
contaminant transport are investigated. One conclusion
from this study indicates that assuming colloid deposition
onto solid matrix to be a linear process is a conservative
assumption if the application of interest is based on the peak
concentration. However, if the first arrival time is the issue
of concern, then a linear colloid deposition assumption may
not be conservative.
References
Abdel-Salam, A., and C. V. Chrysikopoulos (1994), Analytical solutions
for one-dimensional colloid transport in saturated fractures, Adv. Water
Resour., 17, 283 – 296.
Abdel-Salam, A., and C. V. Chrysikopoulos (1995a), Analysis of a model
for contaminant transport in fractured media in the presence of colloids,
J. Hydrol., 165(1 – 4), 261 – 281.
Abdel-Salam, A., and C. V. Chrysikopoulos (1995b), Modeling of colloid
and colloid-facilitated contaminant transport in a two-dimensional frac-
ture with spatially variable aperture, Transp. Porous Media, 20(3), 197 –
221.
Abdul, A. S., T. L. Gibson, and D. N. Rai (1990), Use of humic acid
solution to remove organic contaminants from hydrogeologic systems,
Environ. Sci. Technol., 24, 328 – 333.
Appelo, C. A. J., and D. Postma (1993), Geochemistry, Groundwater and
Pollution, A. A., Balkema, Rotterdam, Netherlands.
Baek, I., and W. W. Pitt (1996), Colloid-facilitated radionuclide transport in
fractured rock, Waste Manage., 16(4), 313 – 325.
Bekhit, H. M. (2004), Contaminant transport in porous media in the pre-
sence of colloids: Numerical and experimental investigations, Ph.D. dis-
sertation, Univ. of Nev., Reno.
Bekhit, H. M., and A. E. Hassan (2005a), Two-dimensional modeling of
contaminant transport in porous media in the presence of colloids, Adv.
Water Resour., 28, 1320 – 1335.
Bekhit, H. M., and A. E. Hassan (2005b), Stochastic modeling of colloid-
contaminant transport in physically and geochemically heterogeneous
porous media, Water Resour. Res., 41, W02010, doi:10.1029/
2004WR003262.
Bekhit, H. M., A. E. Hassan, R. Harris, and C. Papelis (2006), Experimental
and numerical investigations of effects of silica colloids on transport of
strontium in saturated sand Columns, Environ. Sci. Technol., 40, 5402 –
5408.
Bellin, A., P. Salandin, and A. Rinaldo (1992), Simulation of dispersion in
heterogeneous porous formations: Statistics first-order theories, conver-
gence of computations, Water Resour. Res., 28(9), 2211 – 2227.
Bolt, G. H. (1982), Movement of solutes in soils: Principles of adsorp-
tion/exchange chromatography, in Soil Chemistry, Part B: Physico-
Chemical Models, edited by G. H. Bolt, pp. 349 – 386, Elsevier Sci.,
New York.
Bradford, S. A., S. R. Yates, M. Bettahar, and J. Simunek (2002), Phy-
sical factors affecting the transport and fate of colloids in saturated
porous media, Water Resour. Res., 38(12), 1327, doi:10.1029/
2002WR001340.
Buddemeier, R. W., and J. R. Hunt (1988), Transport of colloidal contami-
nants in groundwater: Radionuclide migration at the Nevada Test Site,
Appl. Geochem., 3, 535 – 548.
Champ, D. R., J. L. Young, D. E. Robertson, and K. H. Abel (1984),
Chemical speciation of long-lived radionuclides in a shallow ground-
water flow system, Water Pollut. Res. J. Can., 19(2), 35 – 54.
Chin, D. A., and T. Wang (1992), An investigation of the validity of first-
order stochastic dispersion theories in isotropic porous media, Water
Resour. Res., 28(6), 1531 – 1542.
Chrysikopoulos, C. V., and S. C. James (2003), Transport of neutrally
buoyant and dense variably sized colloids in a two-dimensional fracture
with anisotropic aperture, Transp. Porous Media, 51(2), 191 – 210.
17 of 19
W08409
Coles, D. G., and L. D. Ramspott (1982), Migration of ruthenium-106 in a
Nevada Test Site aquifer: Discrepancy between field and laboratory re-
sults, Science, 215, 1235 – 1237.
Corapcioglu, M. Y., and H. Choi (1996), Modeling colloid transport in
unsaturated porous media and validation with laboratory column data,
Water Resour Res., 32(12), 3437 – 3449.
Corapcioglu, M. Y., and S. Jiang (1993), Colloid-facilitated groundwater
contaminant transport, Water Resour Res., 29(7), 2215 – 2226.
Corapcioglu, M. Y., and S. Wang (1999), Dual-porosity groundwater con-
taminant transport in the presence of colloids, Water Resour Res., 35(11),
3261 – 3273.
Cvetkovic, V. (2000), Colloid facilitated transport by steady random
groundwater flow, Phys. Fluids, 12(9), 2279 – 2294.
Davidson, J. M., and R. K. Chang (1972), Transport of picloram in relation
to soil physical condition and pore-water velocity, Soil Sci. Soc. Am.
Proc., 36, 257 – 261.
DeNovio, M. N., J. E. Saiers, and J. N. Ryan (2004), Colloid movement in
unsaturated porous media: Recent advances and future directions, Vadose
Zone J., 3, 338 – 351.
Dunnivant, F. M., P. M. Jardine, D. L. Taylor, and J. F. McCarthy (1992),
Transport of naturally-occurring dissolved organic carbon in laboratory
columns containing aquifer material, Soil Sci. Soc. Am. J., 56, 437 – 444.
El-Farhan, Y. H., N. M. DeNovio, J. S. Herman, and G. M. Hornberger
(2000), Mobilization and transport of soil particles during infiltration
experiments in an agricultural field, Shenandoah Valley, Virginia, Envir-
on. Sci. Technol., 34, 3555 – 3559.
Enfield, C. G., and B. E. Bledsoe (1975), Fate of wastewater phosphorus in
soil, J. Irrig. Drain. Div. Am. Soc. Civ. Eng., 101, 145 – 155.
Faure, M. H., M. Sardin, and P. Vitorge (1996), Transport of clay particles
and radioelements in a salinity gradient: Experiments and simulations,
J. Contam. Hydrol., 21, 255 – 267.
Fiskell, J. R., S. Mansell, H. M. Selim, and F. G. Martin (1979), Kinetic
behavior of phosphate sorption by acid sandy soil, J. Environ. Qual., 8,
579 – 584.
Flury, M., J. B. Mathison, and J. B. Harsh (2002), In situ mobilization of
colloids and transport of cesium in Hanford sediments, Environ. Sci.
Technol., 36, 5335 – 5351.
Grindrod, P. (1993), The impact of colloids on the migration and dispersal
of radionuclides within fractured rock, J. Contam. Hydrol., 13, 167 – 181.
Grolimund, D., and M. Borkovec (1999), Long-term release kinetics of
colloidal particles from natural porous media, Environ. Sci. Technol.,
33, 4054 – 4060.
Grolimund, D., and M. Borkovec (2004), Colloid-facilitated transport of
strongly sorbing contaminants in natural porous media: Mathematical
modeling and laboratory column experiments, Environ. Sci. Technol.,
39, 6378 – 6386.
Grolimund, D., M. Borkovec, K. Barmettler, and H. Sticher (1996), Colloid
facilitated transport of strongly sorbing contaminants in natural porous
media: A laboratory column study, Environ. Sci. Technol., 30, 3118 –
3123.
Grolimund, D., M. Elimelech, and M. Borkovec (2001), Aggregation and
deposition kinetics of mobile colloidal particles in natural porous media,
Colloids Surf. A, 191, 179 – 188.
Hassan, A., J. Cushman, and J. W. Delleur (1997), Monte Carlo studies of
flow and transport in fractal conductivity fields: Comparison with sto-
chastic perturbation theory, Water Resour. Res., 33(11), 2519 – 2534.
Hassan, A. E., J. H. Cushman, and J. W. Delleur (1998), A Monte Carlo
assessment of Eulerian flow and transport perturbation models, Water
Resour. Res., 34(5), 1143 – 1163.
Hassan, A. E., R. Andricevic, and V. Cvetkovic (2001), Computational
issues in the determination of solute discharge moments and implications
for comparison to analytical solutions, Adv. Water Resour., 24, 607 – 619.
Hornsby, A. G., and J. M. Davidson (1973), Solution and adsorbed fluo-
meturon. concentration distribution in a water saturated soil: Experimen-
tal and predicted evaluation, Soil Sci. Am. Proc., 37, 823 – 828.
Ibaraki, M., and E. A. Sudicky (1995a), Colloid-facilitated contaminant
transport in discretely fractured porous media: 1. Numerical formulation
and sensitivity analysis, Water Resour Res., 31(12), 2945 – 2960.
Ibaraki, M., and E. A. Sudicky (1995b), Colloid-facilitated contaminant
transport in discretely fractured porous media: 2. Fracture network ex-
amples, Water Resour Res., 31(12), 2961 – 2969.
James, S. C., and C. V. Chrysikopoulos (1999), Transport of polydisperse
colloid suspensions in a single fracture, Water Resour Res., 35(3), 707 –
718.
James, S. C., and C. V. Chrysikopoulos (2000), Transport of polydisperse
colloids in a saturated fracture with spatially variable aperture, Water
Resour Res., 36(6), 1457 – 1465.
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS
James, S. C., and C. V. Chrysikopoulos (2003), Analytical solutions for
monodisperse and polydisperse colloid transport in uniform fractures,
Colloids Surf. A, 226, 101 – 118.
James, S. C., T. K. Bilezikjian, and C. V. Chrysikopoulos (2005), Contami-
nant transport in a fracture with spatially variable aperture in the presence
of monodisperse and polydisperse colloids, Stochastic Environ. Res. Risk
Assess., 19(4), 266 – 279, doi:210.1007/s00477-00004-00231-00473.
Johnson, P. R., and M. Elimelech (1995), Dynamics of colloid deposition in
porous media: Blocking based on random sequential adsorption, Lang-
muir, 11(3), 801 – 812.
Johnson, P. R., N. Sun, and M. Elimelech (1996), Colloid transport in
geochemically heterogeneous porous media: Modeling and measure-
ments, Environ. Sci. Technol., 30, 3284 – 3293.
Johnson, W., K. Blue, B. Logan, and R. Arnold (1995), Modeling bacterial
detachment during transport through porous media as a residence-time-
dependent process, Water Resour. Res., 31(11), 2649 – 2658.
Kersting, A. B., D. W. Efurd, D. L. Finnegan, D. J. Rokop, D. K. Smith,
and J. L. Thompson (1999), Migration of plutonium in ground water at
the Nevada Test Site, Nature, 397, 56 – 59.
Kersting, A. B., et al. (2003). Colloid-facilitated transport of low-solubility
radionuclides: A field, experimental, and modeling investigation, Rep.
UCRL-ID-149688, Lawrence Livermore Natl. Lab, Livermore, Calif.
Kim, S. B., and M. Y. Corapcioglu (2002), Contaminant transport in dual-
porosity media with dissolved organic matter and bacteria present as
mobile colloids, J. Contam. Hydrol., 59, 3 – 4.
Kinzelbach, W. (1988), The random-walk method in pollutant transport
simulation, in Groundwater Flow and Quality Modelling, NATO ASI Ser.,
Ser. C Math and Phys. Sci., vol. 224, edited by E. Custodio, A. Gurgui,
and J. P. L. Ferreria, pp. 227 – 246, D. Reidel, Norwell, Mass.
Knabner, P., K. U. Totsche, and I. Kögel-Knabner (1996), The modeling of
reactive solute transport with sorption to mobile and immobile sorbents:
1. Experimental evidence and model development, Water Resour Res.,
32(6), 1611 – 1622.
LaBolle, E., G. Fogg, and A. F. B. Tompson (1996), Random-walk simula-
tion of solute transport in heterogeneous porous media: Local mass-
conservation problem and implementation methods, Water Resour.
Res., 32(3), 583 – 593.
LaBolle, E., J. Quastel, G. Fogg, and J. Gravner (2000), Diffusion processes
in composite porous media and their integration by random walks: Gen-
eralized stochastic differential equations with discontinuous coefficients,
Water Resour. Res., 36(3), 651 – 662.
Leistra, M., and W. A. Dekkers (1977), Some models for the adsorption
kinetics of pesticides, J. Environ. Sci. Health B, 12(2), 85 – 103.
Lyman, W. J., P. J. Reidy, and B. Levy (1992), Mobility and Degradation of
Organic Contaminants in Subsurface Environments, CRC Press,
Chelsea, Mich.
Magee, B. R., L. W. Lion, and A. T. Lemley (1991), Transport of dissolved
organic macromolecules and their effect on the transport of phenanthrene
in porous media, Environ. Sci. Technol., 25, 323 – 331.
Marseguerra, M., E. Patelli, and E. Zio (2001a), Groundwater contaminant
transport in presence of colloids I. A stochastic nonlinear model and
parameter identification, Ann. Nucl. Energy, 28(8), 777 – 803.
Marseguerra, M., E. Patelli, and E. Zio (2001b), Groundwater contaminant
transport in presence of colloids II: Sensitivity and uncertainty analysis
on literature case studies, Ann. Nucl. Energy, 28(18), 1799 – 1807.
McCarthy, J. F., and L. D. McKay (2004), Colloid transport in the subsur-
face: Past, present, and future challenges, Vadose Zone J., 3, 326 – 337.
McCarthy, J. F., K. R. Czerwinski, W. E. Sanford, P. M. Jardine, and J. D.
Marsh (1998a), Mobilization of transuranic radionuclides from disposal
trenches by natural organic matter, J. Contam. Hydrol., 30, 49 – 77.
McCarthy, J. F., W. E. Sanford, and P. L. Stafford (1998b), Lanthanide field
tracers demonstrate enhanced transport of transuranic radionuclides by
natural organic matter, Environ. Sci. Technol., 32, 3901 – 3906.
Mills, W. B., S. Liu, and F. K. Fong (1991), Literature review and model
(COMET) for colloid/metals transport in porous media, Ground Water,
29, 199 – 208.
Nelson, D. M., and K. A. Orlandini (1986), Environmental research divi-
sion progress report 1984 – 85, Tech. Rep. Anl-86-15, Argonne Natl. Lab.,
Argonne, Ill.
Papelis, C., and W. Um (2003), Evaluation of cesium, strontium, and lead
sorption, desorption, and diffusion in volcanic tuffs from Frenchman flat,
Nevada Test Site: Macroscopic and spectroscopic investigations, Desert
Res. Inst., Las Vegas, Nev.
Petersen, C. T., J. Holm, C. B. Koch, H. E. Jensen, and S. Hansen (2003),
Movement of pendimethalin, ioxynil and soil particles to field drainage
tiles, Pest Manage. Sci., 59, 85 – 96.
18 of 19
W08409
Pohll, G., A. E. Hassan, J. B. Chapman, C. Papelis, and R. Andricevic
(1999), Modeling groundwater flow and radioactive transport in a frac-
tured aquifer, Groundwater, 37(5), 770 – 784.
Pohlmann, K., A. E. Hassan, and J. Chapman (2000), Description of hydro-
geologic heterogeneity and evaluation of radionuclide transport at an
underground nuclear test, J. Contam. Hydrol., 44, 353 – 386.
Pohlmann, K. F., A. E. Hassan, and J. B. Chapman (2002), Modeling
density-driven flow and radionuclide transport at an underground nuclear
test: Uncertainty analysis and effect of parameter correlation, Water
Resour. Res., 38(5), 1059, doi:10.1029/2001WR001047.
Ren, J., and A. I. Packman (2004), Modeling of simultaneous exchange of
colloids and sorbing contaminants between streams and streambeds,
Environ. Sci. Technol., 38, 2901 – 2911.
Ren, J., and A. I. Packman (2005), Coupled stream-subsurface exchange of
colloidal hematite and dissolved zinc, copper and phosphate, Environ.
Sci. Technol, 39, 6387 – 6394.
Roy, S. B., and D. A. Dzombak (1998), Sorption nonequilibrium effects on
colloid-enhanced transport of hydrophobic organic compounds in porous
media, J. Contam. Hydrol., 30, 1 – 2.
Ryan, J. N., T. H. Illangasekare, M. I. Litaor, and R. Shannon (1998),
Particle and plutonium mobilization in macroporous soils during rainfall
simulations, Environ. Sci. Technol., 32, 476 – 482.
Saiers, J., and G. M. Hornberger (1996), The role of colloidal kaolinite in
the transport of cesium through laboratory sand columns, Water Resour
Res., 32(1), 33 – 41.
Saiers, J. E., and G. M. Hornberger (1999), The influence of ionic strength
on the facilitated transport of cesium by kaolinite colloids, Water Resour
Res., 35(6), 1713 – 1727.
Saiers, J., G. M. Hornberger, and C. F. Harvey (1994), Colloidal silica
transport through structured, heterogeneous media, J. Hydrol., 163,
271 – 288.
Sardin, M., D. Schweich, F. Leij, and M. T. van Genuchten (1991), Model-
ing the nonequilibrium transport of linearly interacting solutes in porous
media: A review, Water Resour Res., 27(9), 2287 – 2307.
Sen, T. K., S. P. Mahajan, and K. C. Khilar (2002), Colloid-associated
contaminant transport in porous media: 1. Experimental studies, AIChE
J., 48(10), 2366 – 2374.
Sen, T. K., S. Shanbhag, and K. C. Khilar (2004), Subsurface colloids in
groundwater contamination: A mathematical model, Colloids Surf. A,
232, 29 – 38.
Serrano, S. E. (2003), Propagation of nonlinear reactive contaminants in
porous media, Water Resour. Res., 39(8), 1228, doi:10.1029/
2002WR001922.
Short, S. A., R. T. Lowson, and J. Ellis (1988), 234U/238U and 230Th/
234U activity ratios in the colloidal phases of aquifers in lateritic weath-
ered zones, Geochim. Cosmochim. Acta, 52(11), 2555 – 2563.
Sirivithayapakorn, S., and A. Keller (2003), Transport of colloids in satu-
rated porous media: A pore-scale observation of the size exclusion effect
and colloid acceleration, Water Resour. Res., 39(4), 1109, doi:10.1029/
2002WR001583.
Smith, P. A., and C. Degueldre (1993), Colloid-facilitated transport of
radionuclides through fractured media, J. Contam. Hydrol., 13, 143 –
146.
Sun, N.-Z. (1999), A finite cell method for simulating the mass transport
process in porous media, Water Resour Res., 35(12), 3649 – 3662.
Sun, N. (2002), Modeling biodegradation processes in porous media by the
finite cell method, Water Resour. Res., 38(3), 1029, doi:10.1029/
2000WR000198.
Sun, N., M. Elimelech, N. Z. Sun, and J. N. Ryan (2001), A novel two-
dimensional model for colloid transport in physically and geochemically
heterogeneous porous media, J. Contam. Hydrol., 49, 3 – 4.
Tompson, A. F. B., and L. W. Gelhar (1990), Numerical simulation of
solute transport in three-dimensional, randomly heterogeneous porous
media, Water Resour. Res., 26(10), 2541 – 2562.
Totsche, K. U., P. Knabner, and I. Kögel-Knabner (1996), The modeling of
reactive solute transport with sorption to mobile and immobile sorbents:
2. Model discussion and numerical simulation, Water Resour Res., 32(6),
1623 – 1634.
Valocchi, A. J., and A. M. Quinodoz (1989), Application of the random
walk method to simulate the transport of kinetically adsorbing solutes, in
Groundwater Contamination, IAHS Publ., 185, 35 – 42.
van der Zee, S. (1990), Analytical traveling wave solutions for transport
with nonlinear and nonequilibrium adsorption, Water Resour. Res.,
26(10), 2563 – 2578.
van de Weerd, H., A. Leijnse, and W. H. Van Riemsdijk (1998), Transport
of reactive colloids and contaminants in groundwater: Effect of nonlinear
kinetic interactions, J. Contam. Hydrol., 32, 313 – 331.
W08409 BEKHIT AND HASSAN: NONLINEAR CONTAMINANT SORPTION WITH COLLOIDS W08409

van Genuchten, M. T., and R. Cleary (1982), Movement of solutes in soils:
Computer-simulated and laboratory results, in Soil Chemistry, Part B:
Physico-Chemical Models, edited by G. H. Bolt, pp. 349 – 386, Elsevier,
New York.
Villholth, K. G., N. J. Jarvis, O. H. Jacobsen, and H. de Jonge (2000), Field
investigations and modeling of particle-facilitated pesticide transport in
macroporous soil, J. Environ. Qual., 29, 1298 – 1309.
Walton, F. B., and W. F. Merritt (1980), Long-term extrapolation of labora-
tory glass leaching data for the prediction of fission product release under
actual groundwater conditions, Sci. Basis Nucl. Waste Manage., 2, 155 –
166.
Weber, W. J. J., and F. A. DiGiano (1996), Process Dynamics in Environ-
mental Systems, Environ. Sci. Technol., Wiley-Interscience, New York.
Weber, W. J. J., P. M. McGinley, and L. E. Katz (1991), Sorption phenom-
ena in subsurface systems: Concepts, models and effects on contaminant
fate and transport, Water Res., 25(5), 499 – 528.


H. M. Bekhit and A. E. Hassan, Division of Hydrologic Sciences,
Desert Research Institute, 755 E. Flamingo Road, Las Vegas, NV 89119,
USA. (ahmed.hassan@dri.edu)

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