Effects of matrix heterogeneity and aqueous humic acid on transport and

deposition of mineral colloids in sandy sediments

Dien Li
a,
*, Hyun-Shik Chang
b
, John C. Seaman
b
, Daniel I. Kaplan
a
a
Savannah River National Laboratory, Aiken, SC 29808, USA
b
Savannah River Ecology Laboratory, University of Georgia, Aiken, SC 29802, USA
Introduction
A mineral colloid is dened as a system in which nely natural
mineral particles, which are approximately 11000 nm in size, are
dispersed within a continuous medium in a manner that prevents
them from being ltered easily or settled rapidly [1,2]. It has
become increasingly evident that mineral colloids facilitate the
transport of contaminants and radionuclides in subsurface
environments [310]. Therefore, the mechanisms of release,
retention, and transport of colloidal particles in porous media
have been under investigation in recent decades [1125]. Among
these studies, model colloids (e.g., glass spheres) and/or model
porous media (e.g., pure sands) are frequently used in controlled
experiments designed to improve the mechanistic understanding
of colloid fate and transport.
It has been demonstrated that colloid transport and deposit can
be controlled by the degree and type of mineral coatings and their
resulting surface charge heterogeneity in porous media [2631]. As
such, natural colloids isolated from Hanford Site sediments
(Richland, Washington) exhibited greater deposition rates than
kaolinite in both Hanford sediments and a uniformsilica sand [32].
Similarly, the Hanford sediments retained more colloids than did
the silica sand [32]. Lowering solution pH from 7.2 to 4.2 would
neutralize surface charges of natural soil colloids, thereby
increasing colloid deposition and reducing migration through
the silica sands [33]. The inuence of natural organic matter (NOM)
on the natural colloid transport through saprolites has been
investigated [34,35]. Natural soil colloids had high colloidal
stability due to adsorbed NOM; however, when the colloids were
treated with NaOCl to remove adsorbed NOM, colloidal stability
and mobility were greatly decreased. Similarly, humic acid has
been proven to modify the surface charge of engineered nano
particles like apatite [3638], (Hf,Zr)O
2
[39], cerium oxide [30], as
well as mineral colloids [4042], which in turn inuenced colloid
retention and transport through packed sand columns. Despite
these advances in understanding, the transport of mineral colloids
through natural sediments under subsurface groundwater condi-
tions is relatively less well understood because of matrix
heterogeneity, non-spherical colloids, and the presence of oxide/
organic coatings [43]. This knowledge gap compromises our ability
Journal of Environmental Chemical Engineering 1 (2013) 875883
A R T I C L E I N F O
Article history:
Received 22 April 2013
Received in revised form 16 July 2013
Accepted 30 July 2013
Keywords:
Mobile colloids
Deposition
Subsurface sediments
Humic acid
Facilitated contaminant transport
A B S T R A C T
Cellulosic materials, such as paper, cardboard and wood, are commonly co-disposed with low-level
radioactive waste. Cellulosic materials may not only enhance subsurface contaminant transport through
complexation, but also promote colloid dispersion. The objective of this study was to evaluate the effect
of humic acid (HA; as a surrogate for cellulosic materials and natural organic matters) and porous media
heterogeneity on mineral colloid migration through a coarse-textured Savannah River Site (SRS)
sediment or a more uniform Ottawa sand. Positively charged mineral colloids isolated from the SRS
sediment were retained by the Ottawa sand columns. SRS colloids became increasingly more negatively
charged and more stable in suspension with increasing concentrations of HA treatments. There was a
critical HA and mineral colloid concentration ratio of 0.025 above which the transport of colloids was
greatly increased. No quartz or SRS mineral colloids, even those coated with HA, were transported
through the natural SRS sediment due to its heterogeneous surface coatings of goethite/kaolinite and
surface charge properties. Additionally, much fewer mobile colloids were transported through columns
of Ottawa sand with pre-deposited mobile colloids (resembling an aged sediment/mobile colloid
system) than the clean Ottawa sand system. As such, even when conditions favored colloid dispersion
(e.g., elevated pH or HA concentrations), subsequent transport may be limited due to the sediments
natural colloid removal processes caused by coherent particle-sediment attraction and straining.
Published by Elsevier Ltd.
* Corresponding author. Tel.: +1 803 725 7520; fax: +1 803 725 7673.
E-mail address: Dien.Li@srs.gov (D. Li).
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering
j our nal homepage: www. el sevi er . com/ l ocat e/ j ece
2213-3437/$ see front matter . Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.jece.2013.07.032
to predict accurately and numerically model colloid mobilization
and colloid-facilitated contaminant transport under relevant eld
conditions.
The Savannah River Site (SRS) in Aiken, SC contains a nuclear
waste management facility, where low level radioactive waste is
often co-disposed with cellulose-based materials in engineered
cement waste forms, such that a contaminant plume containing
decayed cellulosic materials may develop [44]. Cementitious
leachates have recently been shown to promote the in situ
mobilization of colloid particles from a course-textured SRS
sediment [45,46]. The objective of this study was to quantify
the magnitude of mineral colloid transport through a SRS sediment
under the subsurface conditions of a high organic carbon plume
using column and batch experiments. The effects of humic acid
(surrogate to natural organic matters (NOM)) coating to mineral
colloids and nano mineral attachment to sands on the transport of
mineral colloids through porous media are discussed.
Materials and methods
Articial groundwater (AGW) and sand media
The AGW solution was made based on the monitoring survey
results for uncontaminated groundwater samples at the SRS [47].
Briey, AGW has a pH of 6.0, electrical conductivity (EC) of
0.026 mS cm
1
, turbidity of <1 NTU, and the following chemical
composition: 1.25 mg L
1
Na, 0.25 mg L
1
K, 0.93 mg L
1
Ca,
0.66 mg L
1
Mg, 5.51 mg L
1
Cl, and 0.73 mg L
1
SO
4
2
. The
AGW was designed to mimic non-impacted SRS subsurface
groundwater properties [45,46].
Subsurface sandy sediment was collected from the Tobacco
Road Formation, which is a major formation in the lower vadose
zone and water table aquifer at the SRS. The uncontaminated
course-textured SRS sediment was washed with deionized (DI)
water and sonicated intensively using a Tekmar Sonic Disruptor
(Tekmar Corp., USA) until the supernatant turbidity was <1 NTU,
and then the residual sediments were oven dried at 70 8C. This
washing step was necessary to minimize the release of colloid
particles from the SRS sediment media and their contribution to
the efuent colloid concentrations during column experiments.
Scanning electron microscopy (SEM) indicated that the SRS
sediment was largely comprised of quartz grains that were coated
with patches of goethite and kaolinite. The mean particle grain size
was estimated at 0.45 mm (mean size of 75 sand grains)
(Supplementary data; Fig. S1). Ottawa sand (mean particle grain
size was 0.71 mm; Product #S23-3, Fisher Scientic, USA) was also
washed with DI water until the turbidity of the rinsing solution
was <1 NTU and then oven dried at 70 8C.
Mineral colloid stock suspensions
To create mineral colloid suspensions, the same coarse-
textured SRS sediment used to create the porous media was
mixed with DI water, shaken gently overnight, and then allowed
to settle for 48 h. The remaining suspension was collected and the
AGW stock solution was added at a ratio of 1:1000, which was
designated as the SRS colloidal suspension. The nal colloid
suspension contained 50 mg L
1
colloids, which was close to the
range of mobile colloid suspension concentrations in the SRS eld
[48,49]. Based on XRD analysis, the extracted SRS colloid
suspension consisted of 70% goethite and 30% kaolinite, with
a trace amount of hydroxyl-interlayered vermiculite (Supple-
mentary data; Fig. S2). In addition, the Aldrich HA (Product #
H1675-2) [50] was used to prepare a 200 mg L
1
HA stock
solution, which was ltered (0.1 mm pore size) prior to use. HA
stock solution was added to the SRS colloidal suspensions to
create colloid-stock suspensions with HA concentrations of 1,
1.25, 1.5, 2 and 3 mg L
1
, designated as SRS colloid-HA-N, where N
represents the nal HA concentration. These organic carbon
concentrations are within the range expected in plumes contain-
ing cellulosic degradation products [51]. Similarly, quartz powder
(1.5 mm mean diameter; AGSCO Corp., Wheeling, IL, USA) was
mixed with the AGW solution. After settling for 48 h, the
remaining suspension was collected, which was designated as
the quartz colloid suspension.
The characteristics of the colloidal stock suspensions used for
column transport experiments are given in Table 1. The single most
important distinguishing characteristic of these colloids was their
surface charge, as described by their measured z-potentials. The
SRS colloids had a surface charge of +20.9 mV, the positive charge
originating primarily from goethite coating [46]. However, upon
amending these colloids with HA, there was a surface charge
reversal and the colloids took on a z-potential of 23.1 mV. The
quartz colloids had a net negative charge with a z-potential of
29.8 mV. The pH, EC, and turbidity of each colloid stock solution
were measured before each batch and column experiment. The
colloid concentrations of the quartz and SRS sediment colloids in
working suspensions were approximated through the use of
calibration curves between turbidity and quartz or goethite colloid
suspensions of known concentrations (Supplementary data; Fig.
S3). This method of converting turbidity to colloid concentration is
compromised insofar that the precise mineral assemblages in the
mobile colloid fraction were not used to make these standard
suspensions. In an attempt to use colloid suspensions to create
standards, an unacceptable level of weighing error was realized. As
such, the colloid suspension concentrations reported are only
semi-quantitative.
Tritiated water (200 nCi L
1
) was included in the colloid stock
solutions as a conservative tracer for the column experiments. For
tritiated water analysis, 1 mL of the efuent fractions was mixed
with 10 mL of scintillation cocktail and counted for 20 min (Minaxi
Tri-Carb 4000, Packard Instruments Co.). Breakthrough estimates
were based on relative counts per minute for known dilutions of
the inlet tritiated water solution. A counting error of 2% of the
inlet tritiated water concentration was typically achieved using
this technique.
Table 1
Characteristics of colloid stock solutions.
Characteristics Quartz colloids SRS colloids SRS colloids-HA-2
a
pH 6.60.2 6.40.3 6.80.7
Electrical conductivity (mS cm
1
) 0.021 0.023 0.021
Turbidity (NTU) 475 365 389
Colloid concentration (mgL
1
) 270 49 52
Mean size (nm)
b
4106 39210 36612
z-Potential (mV)
c
29.80.5 +20.91.0 23.10.8
a
SRS colloids amended with 2mgL
1
HA.
b
Determined by dynamic light scattering (ZetaPlus; Brookhaven Instruments Corp., Holtsville, NY).
c
Determined by laser Doppler velocimetry (ZetaPlus). A freshly made SRS colloidal suspension had a pH 5.9 and was used for its z-potential measurement. The pH of the
SRS colloids when used for batch and column experiments was 6.40.3.
D. Li et al. / Journal of Environmental Chemical Engineering 1 (2013) 875883 876
Laboratory batch experiment
Batch experiments were used to study colloidal particle
attachment to the pre-treated Ottawa sand and SRS sediment.
For the kinetic batch experiments, 15.0 g of cleaned SRS sediment
or Ottawa sand was added to 50 mL polypropylene centrifuge
tubes along with 30.0 mL of colloidal stock solutions in AGW.
Control samples were carried through the experiment that
included only AGW solution in contact with the pre-cleaned SRS
sediment or Ottawa sand; no colloid suspension was added. These
non-colloid amended controls were used to monitor the release of
colloids from the pre-cleaned solids. The suspensions were placed
on a reciprocating shaker and the turbidity of the suspensions was
periodically and non-destructively monitored.
For isotherm attachment batch experiments, the cleaned SRS
sediment or Ottawa sand was added at different loadings, ranging
from 1 to 15 g, for each centrifuge tube. About 30 mL of colloidal
stock suspension (50 mg L
1
for the SRS colloids and 470 g L
1
for quartz colloids) were added to each centrifuge tube and then
the tubes were placed on a shaker for 24 h. The turbidity and pH of
the suspension in each tube was measured at the end of this
experiment. As was the case in the above experiment, non-colloid
amended controls were included to monitor the release of colloids
from the cleaned SRS sediment and Ottawa sand. The attachment
coefcient, R
d
(mL g
1
), was calculated using Eq. (1):
R
d

C
0
C
C

V
M
(1)
where C
0
and C are the initial and nal colloid concentrations
(turbidity as the surrogates) in solution, respectively, V is the
volume of batch suspension (mL) and Mis the mass of sand (g) [52].
This equation is similar to that used for solutes and the common
distribution coefcient, K
d
, except that such assumptions as steady
state, innite dilution and no electrostatic interferences between
attached and suspended colloids cannot be made with the R
d
construct.
Laboratory column experiment
The experimental parameters for the transport of mineral
colloids through the Ottawa sand and SRS sediment columns are
summarized in Table 2. The column experimental setup was
similar to that described previously [46]. The column experiments
were performed in three steps at room temperature. First, the
repacked columns were oriented vertically and saturated with
AGW in an upward fashion to eliminate trapped air bubbles. The
columns were ushed with AGWat the owrate of 1 mL min
1
for
70 pore volume (PV) (24 h). Negligible colloid remobilization was
observed during initial column saturation or leaching with the
AGW over the span of 70 PV, as indicated by low efuent turbidity
(<5 NTUfor the pre-treated SRS sediment and <10 NTUfor Ottawa
sand). Second, the colloid stock solutions containing a conservative
tracer were injected into the column upward from the bottom at
the ow rate of 0.35 0.01 mL min
1
for 1318 PV. Column efuent
samples were collected using a fraction collector set to collect 0.25 PV
per tube. The PV estimates were corrected to account for the dead
volumes associated with the inlet and outlet tubing (17.6 mL). As
such, it is expected that the mineral colloids in the treatment efuents
were the un-retained colloids introduced to the column rather than
the indigenous colloids mobilized from the column matrix. Third,
after the colloid suspensions were introduced, just an AGW solution
was added to the columns to observe colloid detachment from the
immobile phase.
Analytical methods
The turbidity, pH, and EC of colloid stock solutions and the
subsequent efuents were measured using a Hach model 2100AN
turbidimeter, a Radiometer Copenhagen PHM 95 pH meter and a
CDM 210 conductivity meter, respectively. The particle size
distribution and z-potential of the inuent suspensions were
measured using ZetaPlus (Brookhaven Instruments Corp., Holts-
ville, NY). The particle size distribution measurement was set for 5
runs, requiring a total of 5 min, and the reported data were
averages of 5 measurements. The z-potential was set to have 10
measurements and the reported data were the averages of the 10
measurements.
Modeling description
The PHREEQC (version 2) model was used to simulate the
colloid behavior in the batch and column experiments. Most
necessary parameters were obtained through the optimization
process based on a manual sensitivity analysis. Kinetic attachment
was described by Eq. (2):
R
i
K
m
C
i

S
i
R
d

(2)
where C
i
is the aqueous concentration of sorbate (mol L
1
), S
i
is the
sorbed concentration (mol g
1
), K
m
is the mass transfer coefcient
(s
1
), and R
d
is the attachment coefcient at steady state (mL g
1
;
Eq. (1)). This equation was adopted from Tebes-Stevens et al. [53],
which was originally derived for solutes. For this study, we
replaced the equilibrium adsorption coefcient, K
d
, with the
attachment coefcient, R
d
, to emphasize that colloids rather than
solutes were involved in the reaction and therefore differences
associated with colloid and solute size would be expected to
inuence colloid attachment [52].
Kinetically controlled straining was the retention mechanism
considered for the simulation of experimental column results
(Eq. (3)):
r
b
u
@S
@t
k
att
C
r
b
u
k
det
S (3)
where C is the aqueous phase concentration for the suspended
colloidal material of interest, S is the sorbed concentration of
colloids, r
b
is the matrix bulk density (g cm
3
), and u is the
volumetric water content (cm
3
), k
att
(s
1
) is the attachment
constant which is closely related to the average grain size of the
matrix and the colloid size, k
det
(s
1
) is the detachment constant
[54]. The tritium breakthrough curve was used for determining
ow velocity (1 m d
1
) and hydrodynamic dispersivity (0.5 cm)
Table 2
Experimental parameters for colloid transport columns.
Cleaned SRS
sediment
Ottawa sand
Column inner diameter (cm) 2.54 2.54
Column length (cm) 15 15
Column volume (cm
3
) 76.0 76.0
Weight of sands (g) 1191.8 1251.2
Bulk density (gcm
3
) 1.570.02 1.640.02
Porosity (%) 27.20.6 27.90.6
Pore volume (cm
3
) 20.61.0 21.21.0
Flow rate for AGW ushing
(mL min
1
)
1.0 1.0
Flow rate for inuent
colloids (mL min
1
)
0.35 0.35
Darcy velocity for inuent
colloids (mday
1
)
1.0 1.0
Residence time (min) 59.01.6 61.01.6
Time interval for sampling
per 0.25 PV (min)
14.81.0 15.31.0
D. Li et al. / Journal of Environmental Chemical Engineering 1 (2013) 875883 877
of the columns. In order to simplify the simulation, the one-
dimensional saturated ow condition was employed. Column
dimensions (length 15 cm, inner diameter 2.54 cm) and porosity
(28%) were considered as xed parameters during transport
simulations. The simulation was conducted only for Ottawa sand
column system because, as discussed in Results and discussion
section, no colloid breakthrough was observed in SRS sediment
columns. The simulation scenario was that the inuent colloid
solution containing tritium was initially introduced into the
column until the breakthrough occurred. Then, the inuent was
switched to water for washing out the column. The treatment
pulse lasted 12.9 PVfor the quartz colloids, and 8.0 PVfor the HA-
treated SRS colloids.
Results and discussion
Mineral colloid attachment
The attachment coefcient, R
d
(Eq. (1)) of quartz colloids (red),
SRS colloids (green) and SRS-colloids-HA-2 (blue) onto Ottawa
sand remained near zero mL g
1
(Fig. 1A). The colloid concentra-
tion ratios (C/C
0
; where C is colloid concentrationin suspensionat a
specic equilibrium time; C
0
is concentration at time zero) for the
quartz colloid and SRS colloids-HA-2 were nearly 100% (Fig. 1B),
indicating that a negligible amount of these colloids were attached
to the Ottawa sand. However, a small fraction (nearly 10%) of the
SRS colloids, in fact, did attach on the Ottawa sand, which was
simulated by the kinetic model (Eq. (2); green line). Amass transfer
coefcient, K
m
, and an attachment coefcient, R
d
, calculated from
this kinetic modeling are presented in Table 3. In contrast, the
retention of the quartz colloids, SRS colloids, and HA-treated SRS
colloids by the SRS sediment increased with time (Fig. 1C and D).
For quartz and SRS colloids, attachment reached the plateau after
8 h. Addition of HA (2 mg L
1
) enhanced the attachment of the
SRS colloids by the SRS sediment, reaching the attachment plateau
at 24 h. The attachment of quartz colloids, SRS colloids and SRS
colloids-HA-2 onto the SRS sediment was modeled (Eq. (2); solid
lines in Fig. 1D), and the optimized K
m
and R
d
are presented in
Table 3. The model simulations quantitatively indicated that,
compared to Ottawa sand, the attachment of the quartz colloids,
SRS colloids, and SRS colloids-HA-2 onto the SRS sediment was
kinetically faster (by comparing K
m
values) and that the attach-
ment capacity (R
d
) of the SRS sediment was nearly two order of
magnitude greater.
The attachment coefcient values of the mineral colloids onto
Ottawa sand or SRS sediment can be largely explained by the
electrostatic behavior of each of the three colloids (Table 1). At pH
6.4, quartz colloids have negatively charged surfaces (29.8 mV),
while the SRS colloids have a more positive charge character due to
the high zero-point of charge of the Fe oxides that coat this

Ottawa sand
Time (hours)
0 10 20 30 40 50
A
t
t
a
c
h
m
e
n
t

c
o
e
f
f
i
c
i
e
n
t

R
d
,

m
L

g
-
1
-1.0
-0.5
0.0
0.5
1.0
Quartz colloids
SRS colloids
SRS colloids-HA-2
Cleaned SRS sandy sediment
Time (hours)
0 10 20 30 40 50
A
t
t
a
c
h
m
e
n
t

c
o
e
f
f
i
c
i
e
n
t

R
d
,

m
L

g
-
1
0
20
40
60
80
Quartz colloids
SRS colloids
SRS colloids-HA-2
A
C
Time (hours)
0 10 20 30 40 50
C
o
n
c
e
n
t
r
a
t
i
o
n

r
a
t
i
o

C
/
C
0
,

%
0
20
40
60
80
100
Quartz colloids
SRS colloids
SRS colloids-HA-2
Model for SRS colloids
B
Time (hours)
0 10 20 30 40 50
C
o
n
c
e
n
t
r
a
t
i
o
n

r
a
t
i
o

C
/
C
0
,

%
0
20
40
60
80
100
Quartz colloids
SRS colloids
SRS colloids-HA-2
Model for Quartz colloids
Model for SRS colloids
Model for SRS colloids-HA-2
D
Fig. 1. Attachment coefcient R
d
(mL g
1
) and suspension concentration ratio (C/C
0
; where C is colloid concentration at a specic equilibriumtime; C
0
is concentration at time
zero) of mineral colloids onto Ottawa sand (A and B) and cleaned SRS sediment (C and D) versus time: quartz colloids (red), SRS colloids (green), SRS colloids-HA (blue) and
calculated SRS colloids (Eq. (2); green line).
D. Li et al. / Journal of Environmental Chemical Engineering 1 (2013) 875883 878
sediment (+20.9 mV). Addition of HA to the SRS colloidal
suspension reversed the surface charge to 23.1 mV. As a result,
quartz colloids and SRS colloids-HA-2 had very little attachment to
the Ottawa sand, while SRS colloids showed slightly more
attachment to Ottawa sand. All three mineral colloids attached
to the SRS sediment presumably because of its heterogeneous
surface charge caused by positively charged goethite coated onto
negatively charged silica sand (Table 1).
Attachment behavior as a function of quartz colloid concentra-
tion for the SRS sediment was evaluated using the Freundlich
adsorption model (Fig. 2A; Eq. (4)):
S K
f
C
1=n
(4)
where S is the colloid mass associated with the solids (SRS
sediment; mg kg
1
), C is the equilibrium colloid concentration in
suspension (mg L
1
), K
f
(L kg
1
or mL g
1
) and 1/n (no unit) is an
empirical constant for a given adsorbate and adsorbent. This
modeling gave K
f
= 161 mL g
1
and 1/n = 0.35 for retention of the
quartz colloids onto the SRS sediment at room temperature
(Fig. 2A), in contrast to the R
d
value 19 mL g
1
in the kinetic
experiment. The low 1/n value indicates that the system is highly
non-linear because 1/n is signicantly different than unity. As 1/n
approaches unity, K
f
approaches a linear isotherm, or the R
d
(or K
d
)
construct. The non-linear behavior may indicate that previously
attached colloids interfere with the subsequent attachment of
additional colloids. This can be attributed to the fact that colloids
have nite size and can block a given portion of the surface
available for adsorption/attachment, a phenomenon commonly
measured and referred to as collector ripening [24], or the
attached colloids altered the surface charge properties on the
immobile phase in such a manner that it reduced the tendency for
subsequent colloids to attach.
For the cleaned SRS sediment, attachment as a function of
colloid concentration is presented in Fig. 2B for the HA-treated SRS
colloids (blue) and the SRS colloids (green). For the SRS colloids-
HA-2, the isotherm is nearly linear and was best described by the
linear R
d
attachment model (Eq. (1)). The R
d
value estimated from
Fig. 2B was 67 mL g
1
, in contrast to the R
d
value derived from the
kinetic experiment (R
d
= 47 mL g
1
). However, the attachment of
SRS colloids onto the SRS sediment is much less than that observed
for the SRS colloid-HA-2, and the isotherm is best described using
the Freundlich model, giving the constants K
f
= 49 mL g
1
and 1/
n = 0.35, in contrast to the R
d
value 24 mL g
1
in the kinetic
experiment.
Mineral colloid transport
The breakthrough curves for quartz colloids (red) and a
conservative tritium tracer (yellow) through an Ottawa sand
column are presented in Fig. 3A. Approximately 65% of the quartz
colloids were transported through the Ottawa sand. Similarly, the
breakthrough curves for SRS colloids (green), HA-treated SRS
colloid-HA-2 (blue) and the tritium tracer (yellow) through an
Table 3
Kinetic modeling for batch and column experiments of mineral colloids onto/through Ottawa sand or SRS sediment.
Mineral colloids Media Batch data modeling (Eq. (2)) Column data modeling (Eq. (3))
Attachment, % Attachment coefcient,
R
d
(mL g
1
)
Mass transfer coefcient,
K
m
(s
1
)
Attachment constant,
k
att
(s
1
)
Detachment constant,
k
det
(s
1
)
Quartz colloid Ottawa sand 0 0 n/a 1.810
7
4.010
6
SRS colloid Ottawa sand 9 0.22 2.010
6
2.510
6a
710
6
SRS colloid-HA-2 Ottawa sand 0 0 n/a 1.310
7
810
6
Quartz colloid SRS sediment 91 19 1.310
5
n/a n/a
SRS colloid SRS sediment 92 24 1.310
5
n/a n/a
SRS colloid-HA-2 SRS sediment 96 47 1.310
5
n/a n/a
SRS colloid-HA-1.5 Ottawa sand 1.810
7
710
6
SRS colloid-HA-3 Ottawa sand 1.410
7
710
6
n/a: no modeling data were available due to either near zero colloid attachment in batches or near 100% colloid retention in columns.
a
The attachment constant might be even larger due to error caused by near 100% colloid retention in the column.

Cleaned SRS sandy sediment

Colloids in solution (mg L
-1
)
0 50 100 150 200 250 300
C
o
l
l
o
i
d
s

a
t
t
a
c
h
e
d

(
m
g

k
g
-
1
)
0
200
400
600
800
1000
1200
Quartz colloid
Y = 160.7 X
0.3467
, R = 0.99
Colloids in solution (mg L
-1
)
0 10 20 30 40
C
o
l
l
o
i
d
s

a
t
t
a
c
h
e
d

(
m
g

k
g
-
1
)
0
200
400
600
800
1000
1200
SRS colloid
Y = 48.79 X
0.3528
, R = 0.98
SRS colloid-HA-2
Y = 66.63 X, R = 0.98
A B
Fig. 2. Attachment of mineral colloids onto pre-treated SRS sediment in AGW as a function of colloid concentration after equilibration for 24 h: (A) quartz colloids (red); (B)
SRS colloids (green) and SRS colloids-HA-2 (blue).
D. Li et al. / Journal of Environmental Chemical Engineering 1 (2013) 875883 879
Ottawa sand column are presented in Fig. 3B. The SRS colloids were
completely retained in the column, which is likely related to
electrostatic attraction between the positively charged surfaces of
the SRS colloids and the slightly negative charge of the Ottawa sand
(Table 1), as well as colloid straining under the current
experimental conditions. The colloid straining may even played
a more signicant role than the surface charges. However, with
addition of 2 mg L
1
HA to the SRS colloids, nearly 80% of the HA-
treated SRS colloids were transported through the Ottawa sand
column and simulated using a kinetically controlled straining
model (Eq. (3); red line). In this case, the colloid surface charge
reversal promoted increasing electrostatic repulsion between the
negatively charged colloidal particles and Ottawa sand grains
(Table 1). This trend is in agreement with the batch attachment
experiments (Fig. 1).
The kinetically controlled straining model (Eq. (3)) simulated
well the breakthrough proles for the quartz colloids (red line in
Fig. 3A) and SRS colloids-HA-2 (blue line in Fig. 3B), and the slow
increase of the colloid concentration after breakthrough and the
tailing observed during the subsequent washing period. The
optimized kinetic parameters, k
att
and k
det
, calculated by model
simulations to the experimental data are presented in Table 3. The
errors for the kinetic parameters given in Table 3 are in the order of
10%, estimated from the duplicate column experimental data of the
same mineral colloids. The attachment coefcient, k
att
, for the SRS
colloids was nearly 20 times larger than those for quartz colloids and
SRS colloids-HA-2, and thus the SRS colloids had a lower transport
percentage through Ottawa sand than both quartz colloids and SRS-
colloids-HA-2, in agreement with the surface charge properties of the
mineral colloids. Under similar unfavorable attachment conditions,
the SRS colloid-HA-2 had a higher transport percentage than the
quartz colloids, which may be related to the quartz colloids larger
particle size, more angular particle shape (SEM images not
presented). Together these properties would result in a greater
straining of the quartz colloids than the SRS colloids-HA-2 [1114].
Colloid transport behavior observed for the cleaned SRS
sediment column matrix (Fig. 3C and D) was in sharp contrast
with results for the Ottawa sand columns in that the quartz
colloids, SRS colloids, and SRS colloids-HA-2 were all retained.
These results can be explained by two mechanisms. First, the SRS
sand grains, although initially cleaned by sonication, were still
heterogeneously coated by patches of mineral particles, including
positively charged goethite and negatively charged kaolinite
[45,46]. As a result, the inuent colloids, regardless of their
surface charge properties, were retained by the SRS sediment.
Second, kinetically controlled model simulations indicate that
straining played an important role in the colloid retention in the
SRS sediment. Under similar conditions, the straining of mineral
colloids in the SRS sediment is likely much greater than for the
Ottawa sand, because of its greater range of particle sizes and
dissimilar particle shapes (based on SEM images), and complex
pore structure [1114,5557].

Ottawa sand
Number of pore volume
0 2 4 6 8 10 12 14 16 18
C
/
C
0
,

%
0
20
40
60
80
100
Quartz colloids
Tritium
Model for Quartz colloids
Model for tritium
Number of pore volume
0 2 4 6 8 10 12 14
C
/
C
0
,

%
0
20
40
60
80
100
SRS colloids
SRS colloids-HA-2
Tritium
Model for SRS colloids-HA-2
Model for tritium
Cleaned SRS sandy sediment
Number of pore volume
0 2 4 6 8 10 12 14
C
/
C
0
,

%
0
20
40
60
80
100
Quartz colloids
Tritium
Number of pore volume
0 2 4 6 8 10 12 14
C
/
C
0
,

%
0
20
40
60
80
100
SRS colloids-HA-2
Tritium
SRS colloids
A
C
B
D
Fig. 3. Breakthrough proles of mineral colloids through porous media versus number of pore volumes, where the yellowtriangles represent tritiated water (i.e., conservative
tracer): (A) quartz colloids (red) through Ottawa sand; (B) SRS colloids (green) and SRS colloids-HA-2 (blue) through Ottawa sand; (C) quartz colloids (red) through SRS
sediment; (D) SRS colloids (green) and SRS colloids-HA-2 (blue) through cleaned SRS sediment.
D. Li et al. / Journal of Environmental Chemical Engineering 1 (2013) 875883 880
Effect of matrix heterogeneity
In order to understand further how the heterogeneous
deposition of colloid particles on a sand collector would inuence
the transport of the inuent colloids, the column was initially
repacked with pure Ottawa sand and then injected with SRS
colloids for 65 PV. As expected, all untreated SRS colloids were
retained in the Ottawa sand column, which led to the normalized
concentration of retained SRS colloids of 0.54 mg g
1
of Ottawa
sand. The breakthrough curve of the SRS colloids-HA-2 through the
Ottawa sand with the pre-retained SRS colloids (red circles), in
comparison with pure Ottawa sand (blue diamonds), is presented
in Fig. 4. For pure Ottawa sand (blue), 75% of the injected SRS
colloids-HA-2 was transported and the breakthrough curve formed
a plateau. In contrast, for the Ottawa sand with the pre-retained
colloidal goethite and kaolinite and then with increased surface
heterogeneity, the breakthrough curve of the SRS colloids-HA-2
was asymmetrical without a plateau, and the amount of
transported colloids decreased to 30%. It appears that as more
colloidal goethite and kaolinite were retained in the Ottawa sand
column, the amount of subsequent SRS colloids-HA-2 transported
through the column further decreased substantially. These results
suggest that suspended colloids originating from a high NOM
plume may be originally highly mobile, but as colloids become
attached to the matrix, the tendency for the mobile colloids to be
transported through the column decreases. As a result, the SRS
sediment, which is naturally heterogeneously coated with goethite
and kaolinite, would have a high capability of ltering the colloids
of either positive or negative surface charges, and of highly
retarding the colloid transport.
Effect of humic acid
Fig. 5 shows the breakthrough curves for SRS colloids-HA
treated with different amounts of HA passing through Ottawa sand
columns, which were simulated using the same kinetically
controlled straining model (Eq. (3)) (Fig. 5A). The kinetic
attachment (k
att
) and detachment (k
det
) constants calculated by
this modeling are presented in Table 3. The uncertainties of the
calculated kinetic parameters were estimated to be 10%, based on
the duplicate column experiments. Fig. 5C shows the average relative
colloid concentration C/C
0
(%) of the breakthrough curve plateau as a
function of the amount of HA (mg L
1
) added. The SRS colloids were
essentially all retained in the Ottawa sand column when the added
HA concentrations of the injected colloids were 1.25 mg L
1
(or HA
to colloid ratio of 0.025). However, at the HA concentration of
1.5 mg L
1
, 5265% of the SRS colloids were transported through the
Ottawa sand. At an HA concentration of 2 mg L
1
, the amount of the
SRS colloids transported through Ottawa sand reached 75% for each of
the duplicate columns.
In a separate experiment, the stability of the HA-treated SRS
colloid suspensions in AGWwere monitored for one week, and the
mean particle size (circles) and z-potential (squares) of these SRS
colloid suspensions were measured (Fig. 5B). With addition of HA
to the SRS colloid suspension, the measured mean size increased
from 392 to 815 nm at the HA content of 0.6 mg L
1
, due to
agglomeration caused by neutralization of surface charge of the
SRS colloid suspension. After that, the measured particle sizes
decreased to 388 nmat the HAcontent of 3 mg L
1
. Meanwhile, the
measured z-potential changed from +20.9 mV for the untreated
SRS colloid to increasingly more negative 26.9 mV at the HA
content of 3 mg L
1
. These results were consistent with the
observed dispersion and stability of the SRS colloid suspensions,
which may be attributed to both electrostatic and steric stabiliza-
tion.
The measured breakthrough curves of the HA-treated SRS
colloids are related to three factors colloidal particle morphology
and straining, colloid and sediment surface charges, colloid size
and stability. The addition of HA to the SRS colloids signicantly
reduced the straining effect and thus decreased the deposition of
the treated SRS colloids in the Ottawa sand columns. The untreated
SRS colloids in AGW are fairly stable, because of highly positive
surface charge; however, they were completely retained in the
Ottawa sand column, because of the opposite surface charges
between the untreated SRS colloids and Ottawa sand collector. The
HA treatment of the SRS colloids reversed their surface charge, the
colloidal particles became agglomerated at the HA content
<0.6 mg L
1
, due to the relatively low surface charge, the colloids
were deposited in the Ottawa sand columns. At the HA contents of
0.61.25 mg L
1
, the surface charge of colloids became just slightly
more negative, the dispersion and stability of the colloids
increased, but they were not stable long enough. This behavior
may indicate that the steric repulsion may play a more signicant
role in the stabilization of colloids with the increased HA contents.
At the HA concentration of 2 mg L
1
, the SRS colloids displayed the
highest negative z-potential and appeared to be the most stable
dispersion, as a result, the colloids had the lowest deposition rate
and highest breakthrough rate of 75%. Presumably this may be
related to the optimized stability of colloids due to electrostatic/
steric stabilization [3442], and reduced straining [1113] at the
higher HA concentration (e.g., 2 mg L
1
).
Environmental implication
Cementitious materials are increasingly used as engineered
barriers and waste forms for radiological waste disposal, like at the
SRS site. Extreme alkaline pH environments of cementitious
leachate plumes may change mineral surface charges, temporarily
promoting the formation of mobile colloids [46]. This study under
the experimental conditions demonstrates that even if mineral
colloids are mobilized, e.g., by a plume containing cementitious
leachate or cellulosic degradation products, subsequent migration
may be limited. The sediment can naturally lter mineral colloids
due to coherent particle-collector attraction and straining.
Furthermore, the colloid-facilitated transport of radionuclides
through the subsurface sediments would be restricted.
In broader applications, a novel nding fromthis study was that
batch experiments can provide insight into the attachment
behavior of mineral colloids onto sand media, like the adsorption
of bacteria or virus onto solid surfaces [52]. The colloid attachment
behavior onto a media can be at least semi-quantitatively

SRS colloids-HA-2
Number of pore volume
0 2 4 6 8 10 12 14
C
/
C
0
,

%
0
20
40
60
80
100
SRS colloids-retained Ottawa sand
Pure Ottawa sand
AGW
Fig. 4. Breakthrough curves of SRS colloids-HA-2 introduced into cleaned Ottawa
sand and Ottawa sand that contained attached SRS colloids (0.54 mg colloids per g
of cleaned Ottawa sand).
D. Li et al. / Journal of Environmental Chemical Engineering 1 (2013) 875883 881
simulated using kinetic models, similar to solute adsorption onto a
solid surface, and might predict the transport behavior of the
colloids in the similar porous media columns or the subsurface
sediments [1114]. Both the attachment and transport behavior of
mineral colloids are closely related to their surface charge and the
resulting suspension stability. For the media like the washed SRS
sediment and more uniform quartz sand, the mineral colloid
retention might be controlled by the surface properties of mineral
colloids in the relevant systems, such as electrostatic surface
charges, surface morphology, heterogeneous coating by other nano
minerals or organic matters [3035,4042,5557]. However, it is
unknown yet how the colloid retention may be related to physical
or hydrological ow properties in the natural environment.
Conclusions
The presence of HA in the subsurface sediments can increase
the dispersion and mobility of mineral colloids, which potentially
increases the risk that the metal contaminants and radionuclides
are transported through these systems. The HA and colloid
concentration ratio of 0.025 (or 1.25 mg L
1
HA per 50 mg L
1
colloids) appeared to be a critical threshold, above which the
transport of colloids through Ottawa sand column is greatly
increased. Furthermore, the transport of colloids is much slower
through a matrix with heterogeneous deposition of colloids than
through clean matrix materials. Thus, a working conceptual model
is that the attached colloids might create additional attachment
sites and clog pores, reducing the ow of subsequent colloids
through the porous media.
Acknowledgements
This work was supported by Department of Energy, Environ-
mental Management. Work was conducted at the Savannah River
National Laboratory under the U.S. Department of Energy Contract
DE-AC09-96SR18500. Participation of Dr. J.C. Seaman and Dr. H.S.
Chang in the current study was supported by the Savannah River
Ecology Laboratory through a Financial Assistance Award DE-
FC09-07SR22506 from DOE to the University of Georgia Research
Foundation.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jece.2013.07.032.
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Number of pore volume
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C
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,

%
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SRS colloids-HA-3
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