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Applied Clay Science 21 (2002) 59 – 66

www.elsevier.com/locate/clay

Application of a geochemical transport model to predict


heavy metal retention (Pb) by clay liners
Ray E. Ferrell a,*, Per Aagaard b, Johan Forsman a, Lea Greenwood a, Zuoping Zheng b
a
Department of Geology and Geophysics, Louisiana State University, Baton Rouge, LA 70803, USA
b
Department of Geology, University of Oslo, Oslo, Norway
Received 25 October 2000; received in revised form 2 February 2001; accepted 16 July 2001

Abstract

PHREEQC, a geochemical transport model, is used to simulate diffusive transport of Pb through a 10-cm-thick clay liner.
The results are compared to those of Roehl and Czurda [Applied Clay Science 12 (1998) 387] who studied Pb migration by
diffusion in a carefully monitored laboratory experiment. The computer simulation accounts for effects due to adsorption by ion
exchange, changes in CEC, variable ion selectivity, and porosity or compacted density. It facilitates evaluation of changes in the
diffusion coefficient and solution input parameters. The effective Pb diffusion coefficient determined for the simulation is
3  10  10 m2 s  1 and for the 520-day experiment of Roehl and Czurda it is 2.3  10  10 m2 s  1. Differences in the
retardation factors (23.6 and 503, respectively) indicate that the model does not account for all of the adsorption mechanisms
suggested by the experimental investigation. Thus, less Pb is retained and the liner is predicted to fail more rapidly than the
actual results indicate. Models have great flexibility, but need to be verified by field data before they can be applied to specific
waste site conditions. D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Transport; Lead; Clay liner; Diffusion

1. Introduction isolation of high-level nuclear wastes (Madsen, 1998).


Computer models incorporating the results of modern
Geochemical transport models have great utility in studies of reaction mechanisms provide the opportu-
assessing the retention of potential heavy metal con- nity to examine factors affecting waste retention and
taminants by clay liners. Natural and compacted clay- offer the potential to identify those factors that are
rich materials and geosynthetic textiles containing most likely to influence the integrity of natural and
clay minerals are among the most commonly em- engineered clay barriers. Several models (Selim, 1992)
ployed methods to isolate landfill wastes from the based on the assumption of local equilibrium are
environment. Clay liners are particularly important available to assess processes such as ion exchange,
with respect to the role that they may play in the complexation, and competitive adsorption. Others
have developed multireaction – multisite models incor-
porating varying kinetic effects and irreversible reac-
*
Corresponding author. Fax: +1-225-578-2302. tions (Selim, 1992; Hinz et al., 1992). One of the most
E-mail address: rferrell@lsu.edu (R.E. Ferrell). thorough laboratory and field studies of Cd, Pb, Zn

0169-1317/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 1 3 1 7 ( 0 1 ) 0 0 0 9 2 - 8
60 R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66

and Cr diffusion and sorption by clay minerals is that Table 1


reported by Wagner (1992). Typical input for simulation of diffusive flux through a clay barrier
(Pb) with ion exchange
PHREEQC (Parkhurst, 1995) is one of the com-
SOLUTION 1 – 20
puter programs for geochemical reaction modelling in
-units mmol/kgw
common use. Based on an ion-association aqueous Ca 0.9
model, it can perform speciation and saturation index Na 0.1
calculations; simulate reaction-paths and 1D-transport Alkalinity 1.7 as HCO3
involving reversible reactions, and inverse modelling Cl 0.2
EXCHANGE 1 – 20
of reactions to account for differences in composition
X 1.0
between waters. Reactions considered include those -equil 1 – 20
involving aqueous, mineral, and gaseous phases; EXCHANGE_SPECIES
solid-solution, surface complexation and ion-ex- Pb + 2 + 2X  = PbX2
change equilibria; and irreversible reactions involving log_k 1.05
END
specified mole transfers of reactants, kinetically con-
SOLUTION 0
trolled reactions, mixing of solutions, and temperature -units mmol/kgw
changes. The latest version of PHREEQC (Parkhurst pH 6
and Appelo, 1999) includes capabilities to simulate Pb 1
dispersion or diffusion in 1D-transport calculations, Cl 2
END
with or without advective transport. A WINDOWS
TRANSPORT
version of PHREEQC prepared by Vincent Post may -cells 10 #number of cells
be obtained free of charge from the website, http:// -length 0.01 #length (m) of cells
www.geo.vu.nl/users/posv/phreeqc.html. -flow_direction diffusion_only
The purpose of this paper is to illustrate the use of -shifts 1 #value times time_st is total time for
diffusion calculation
PHREEQC to simulate changes in clay content, cation
-diffc 3.0e  10 # diffusion coefficient = 3.0e  10 m2/s
exchange capacity, metal concentration, ion exchange -bcon constant flux
and other factors on the diffusive transport of Pb -time_st 3.15e7 #1 year
through a 10-cm barrier. Diffusion may be the most USER_GRAPH
important transport processes when the permeability is -heading Distance/m Cl Cd CdX2 CaX2 NaX
-axis_scale x_axis 0 1
about 1  10  9 m s  1 (Shackelford, 1991). All
-axis_scale y_axis 0 1
calculations were performed without advective trans- -axis_titles Distance/m mol/l
port, thus focusing on reactions within the liner. The -chart_title
results represent the best-case situation when com- -initial_solutions false
pared to actual waste repositories, as some advective -start
10 graph_x Dist
transport is often observed (Johnson et al., 1989).
20 graph_y tot(‘‘Cl’’) * 1e6, tot(‘‘Pb’’) * 1e6,
Computed results are compared with the experimental mol(‘‘PbX2’’) * 1e6, mol(‘‘CaX2’’) * 1e6, mol(‘‘NaX’’) * 1e6
results of Roehl and Czurda (1998) for Pb in order to -end
assess the validity of the model assumptions. END

2. Methods
example, a low ionic strength calcium –sodium bicar-
2.1. Simulation conditions bonate –chloride solution has been used to represent
the initial composition of the pore water in the barrier.
PHREEQC commands for simulation of Pb trans- The solution contained 0.9 mmol/kgw Ca, 0.1 mmol/
port by diffusion are presented in Table 1. The major kgw Na, 0.2 mmol/kgw Cl and alkalinity of 1.7 mmol/
command blocks are identified with all upper case kgw expressed as HCO3. The amounts and types of
letters. SOLUTION is used to define the temperature exchangers are defined in the EXCHANGE block. X
and composition of up to 20 initial solutions. In this equals the CEC (equivalents per liter) of the
R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66 61

exchanger utilised in these simulations and CaExch A third effect attributable to changes in the char-
initially occupies more than 99% of the exchange acter of the clay or clay minerals can be simulated by
sites. Half reactions and relative log k values for changing the apparent exchange constant for the
exchange reactions are defined next. This block metal/exchanger half-cell with regard to the Na/
(EXCHANGE_SPECIES) is ordinarily left blank exchanger half-cell used as the reference reaction
and values in the database file are used automatically. (log k = 0.0). For example, changing the log k for Pb
Alternatively, the user can identify new half reactions exchange from 1.05 to 0.0 will eliminate the specific-
or modify the relative log k. SOLUTION 0 establishes ity of the exchanger for the Pb ion and Na and Pb
the composition of the input fluid. In this case, it is a exchange will proceed as a linear reaction.
pH 6.0 PbCl2 solution containing 1 mmol/l of the
metal. Conditions for the TRANSPORT calculations 2.3. Initial concentration of metal
are established next. The cell was divided into 10
segments 0.01 m in length, the effective diffusion The effects of initial metal concentration in the
coefficient (Deff) was 3  10  10 m2 s  1 and the input solution on values associated with a given depth
experiment was conducted for 3.15  108 s, or 10 in a penetration profile can be determined from Fick’s
years. Deff is often used to represent the diffusion second law of diffusion. The partial differential equa-
coefficient derived from laboratory or field determi- tion can be integrated to obtain a solution (Appelo and
nations of element profiles. It is equal to the product Postma, 1994) for the concentration of a mobile
(Roehl and Czurda, 1998) of the free solution diffu- component at a given point and time that can be
sion coefficient (D0) and the tortuosity factor (s) expressed in terms of the initial or boundary condi-
divided by the retardation factor (R). Graphing and tions. Increasing the input concentration increases the
output conditions are established in the last block. concentration or apparent rate of penetration at a
END statements throughout signify the end of each given point.
input block.

2.2. Variable clay properties 3. Results

The influence of changes in clay type on the metal 3.1. Ion exchange capacity
diffusion profile can be simulated in three ways.
Variations in the total quantity of clay and the type Increasing clay content or the CEC of the clay
of clay can be used to modify the total sample CEC. produces the changes in the apparent penetration
Ten weight percent clay with a CEC of 100 meq/100 g profile of a metal illustrated in Fig. 1. In this diagram,
is equivalent to 50 wt.% clay with a CEC of 20 meq/ results for 10 years of diffusion are compared for
100 g. Porosity (e) and bulk density (qb) also influ- initial exchange capacities varying from 0.5 to 2.0
ence the available cation exchange capacity. CEC in equivalents/l. The highest value is equivalent to a
meq/l can be obtained by multiplying the value sample with a CEC of 41 meq/100 g with 35%
measured as meq/100 g by 10  qb/e (Appelo and porosity and a density of 1.7 g/cm3. This represents
Postma, 1994). A sample with a CEC of 18.5 meq/100 a solid with 100 wt.% of a high CEC illite or
g with a bulk density (qb) of 1.68 g/cm3 and a porosity vermiculite, or 41 wt.% smectite with a CEC of 100
(e) of 35% will have a CEC of 885 meq/l. Increasing meq/100 g mixed with a material with no ion
this value increases the quantity of an element exchange capacity. Profiles shown depict changes in
adsorbed by the solids and thus increases the effective exchangeable Ca and Pb plus Cl and Pb in the pore
retardation. Converting CEC to a constant volume fluid. Exchangeable Na is not illustrated because the
facilitates comparison with the quantities of elements values are smaller than 0.0001 mol/l. After 10 years,
in the pore solution and mass transfer associated with Pb occupies 50% of the exchange sites (0.5 mol PbX2)
reaction and transport through the clay. In most of the at a depth of 1.0 cm when the CEC is 2 equivalents/l
simulations described below, the exchange capacity (Fig. 1A). The depth to 50% exchangeable Pb
was either 1.0 or 1.1 mol of a univalent exchanger/l. increases to 1.4 and 2.0 cm, respectively, when the
62 R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66

3.2. Ion exchange selectivity

Ion exchange selectivity can be modelled by mod-


ifying the log k of the element with regard to the
reference half-cell. Changes in the relative ion
exchange constant for Pb produce the effects shown
in Fig. 2. After 10 years of diffusion, there is less ion
exchange when the relative ion exchange constant for
the Pb half cell (log k = 0.1) is close to that for Na. The
system retains a strong selectivity for Ca. The depth to
50% Pb exchanged decreases from 1.4 to 0.9 and 0.3
cm as the relative log k changes from 1.05 to 0.53 to
0.1 (Fig. 2A). The change in adsorption is accompa-
nied by a change in the depth to the Pb C/Co of 0.1

Fig. 1. Changes in Pb penetration profiles associated with variable


total cation exchange capacity (CEC) of the simulated liner. (a)
Exchangeable Ca and Pb at total exchange capacities of 0.5, 1.0 and
2.0 mol/l. (b) Pb and Cl in solution with one of the exchangeable Pb
values reproduced for comparison with a.

exchange reservoir is reduced to 1.0 and 0.5 equiv-


alents/l. Cl in solution (Fig. 1B) has reached a steady
state equal to the input value in all cells because it is a
conservative element and is not involved in the
simulated reactions. The diamond-shaped data points
for ExcPb in the 0.5 equivalents/l simulation illustrate
how much more Pb is held in exchange positions than
in pore fluids. Depth of penetration for Pb in the pore
fluid (SolPB) varies inversely with the CEC of the Fig. 2. Changes in Pb penetration profiles associated with variable
log k for Pb exchange in the simulated liner. (a) Exchangeable Ca
liner material. The depth to C/Co of 0.1 is 4.3, 2.7, and and Pb by clays with relative log k of 0.1, 0.53 and 1.05 with respect
2.0 cm when the CEC is 0.5, 1.0, and 2.0 equivalents/ to Na. (b) Pb and Cl in solution with one of the exchangeable Pb
l, respectively. values reproduced for comparison with a.
R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66 63

(Fig. 2B). Decreasing the relative log k decreases the


adsorbed Pb, so the apparent migration takes place
more rapidly. Depths to C/Co of 0.1 are 2.7, 4.5, and
7.5 cm, respectively. Exchangeable Pb is still signifi-
cantly higher than the quantity in solution. When the
barrier material has a stronger preference for the
naturally occurring elements in the pore fluid, the
metal contaminant will migrate more rapidly than
when there is a strong ion exchange preference for
the metal.

3.3. Effective diffusion coefficient

Changes in the effective diffusion coefficient uti-


lised in the simulation produce the changes in the
penetration profiles illustrated in Fig. 3 after 10 years
of transport. As the coefficient increases from 1.5 to
3.0, and 6.0  10  10 m2 s  1, the depth to 50%
exchangeable Pb increases to 1.5, 1.9, and 2.4 cm,
respectively (Fig. 3A). The depth to C/Co of 0.1 for Pb
in the pore fluid also increases from 1.8, 2.4, and 3.8
cm (Fig. 3B) A 4  increase in the diffusion coef-
ficient increases the rate of Pb penetration about 2  .

3.4. Input fluid composition

Increasing the concentration of Pb in the input fluid


increases the depth of Pb penetration as shown in Fig.
Fig. 3. Changes in Pb penetration profiles associated with variable
4. When Pb is 0.1 mmol/l and the ion exchange effective diffusion coefficients (m2 s  1). (a) Exchangeable Ca and
capacity is 1.0 equivalent/l, exchangeable Pb is only Pb with coefficients of 1.5e  10, 3.0e  10, and 6.0e  10 m2 s  1.
detectable in the first centimeter of the cell. When Pb (b) Pb and Cl in solution with one of the exchangeable Pb values
in the input solution is 10.0 mmol/l, the depth to the reproduced for comparison with a.
50% exchangeable level increases to 3.7 cm (Fig. 4A).
At this high concentration level, Pb is no longer
confined to the simulated liner and C/Co in the last more linear and effects similar to those illustrated in
cell of the barrier is 0.3 (Fig. 4B). Increases in the Pb Fig. 2 are observed. A 10  increase in millimoles of
concentration in the input solution satisfy the demands Na and Ca in the pore fluid increases the mole fraction
for ion exchange more rapidly. Subsequently, the of Na in the exchanger from < 0.01 to almost 0.04, so
build up and transport through the pore network is the magnitude of the expected change in Pb retention
more rapid. is small.

3.5. Ionic strength of pore fluid 3.6. Summary of modelling results

The chief consequence of increasing the ionic The results of the transport simulations described
strength of the pore fluid is a decrease in the apparent above illustrate several of the basic principles govern-
selectivity of the ion exchanger for the ions that are ing the retention of metal wastes by clay liners. The
more strongly attracted to the exchanger at low con- magnitude and selectivity of the ion exchanger has a
centrations. The exchange relative to Na becomes major effect on the retardation of diffusing wastes.
64 R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66

 Rate of metal penetration is directly related to


increases in its concentration in the input
solution.
 Large changes in the composition of the pore
fluid produce minor changes in the mole
fraction of weakly adsorbed ions, thus creating
the potential for minor increases in metal
penetration rate.

3.7. Comparison with experimental results

The experimental results obtained by Roehl and


Czurda (1998) for Pb provide an excellent basis for
comparison with PHREEQC simulations. The authors
assessed the retardation and solid speciation of Pb
(also Cd) migrating into an illitic/smectitic loess loam
during experiments lasting from 43 to 520 days. The
loam had a CEC of 18.5 meq/100 g and experiments
were performed at a Proctor density of 1.68 g/cm3 at
moisture content of 17.5 wt.%. Calculated apparent
diffusion coefficients for input solutions containing
0.001 M Pb or Cd chloride were in the range of 3.6–
7.4  10  9 cm2 s  1 for Pb and 4.9– 6.7  10  8
cm2 s  1 for Cd, with a slight tendency to decrease
with the length of the experiment. The bulk of the
adsorbed metal was in the fraction defined as ex-
changeable (60 – 80%) by selective sequential extrac-
tion procedures. The operationally defined carbonate
fraction (representing specific fixation on pH-depend-
ent sites) was next most abundant.
Fig. 4. Changes in Pb penetration profiles associated with variable
Pb content and ionic strength of the simulated waste. (a)
Exchangeable Ca and Pb at total Pb concentrations of 0.1, 1.0,
and 10.0 mol/l. (b) Pb and Cl in solution with one of the
exchangeable Pb values reproduced for comparison with a.

Important relationships controlling diffusive transport


include:

 Increased CEC of the barrier materials retards


metal movement.
 Increased clay content increases the effective
CEC and thus promotes retardation.
 When the clay has a strong exchange preference
for an ion in the waste fluid compared to those
naturally present in the pore fluids of the barrier,
the input ion movement will be strongly retarded. Fig. 5. Comparison of simulated Pb penetration profiles with data
 Increasing the effective diffusion coefficient (open circles and triangles) from the 520-day experiment of Roehl
increases the rate of penetration. and Czurda (1998).
R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66 65

Table 2 differences between the simulated and experimental


Calculated retardation factors (R) results are most obvious with respect to R and Dapp. R
C/Co Cl distance (cm) Pb distance (cm) R (Pb) is a dimensionless retardation factor reflecting the
0.01 50.0 3.65 13.7 relative rate of transport of a non-reactive solute to a
0.1 31.2 1.4 22.3 reactive one. The apparent diffusion coefficient (Dapp)
0.5 13.7 0.58 23.6
is the parameter that most closely approximates the
movement of a reactive solute through a particular
A comparison of the Roehl and Czurda (1998) data soil. Dapp is the value that is often used to compare
for the 520-day experiment with PHREEQC-simu- element behaviour in different samples, but is mean-
lated Pb pore fluid profiles is presented in Fig. 5. The ingless without an estimate of the retardation factor.
simulations were conducted with a CEC of 18.5 meq/ The factors are related by:
100 g, bulk density of 1.68, porosity of 36% and the
other input parameters identified in Table 1. Pb input Dapp ¼ Deff =Retardation ðRÞ
was constant and the bottom of the column was open.
Pb concentrations were modified by ion exchange Differences in the estimate of the retardation factor
with a relative log k of 1.05. Effective diffusion account for the large differences in the apparent dif-
coefficients (D eff ) were 1.0, 3.0, 4.0, 5.0 and fusion coefficient derived from the experiment and the
6.0  10  10. The best visual fit to the experimental simulation. A good estimate of this R is critical when
data was obtained with Deff = 3.0  10  10 m2 s  1. attempting to evaluate the retention of Pb by clay liners.
Deff reported by Roehl and Czurda (1998) from other R is different in the two instances described above
laboratory experiments was 2.3  10  10 m2 s  1. because it is calculated differently. Roehl and Czurda
The two values are essentially equal. (1998) used actual determinations of Pb in the soil and
Retardation (R) in the simulation was evaluated at an independent experimental determination of Deff to
several values of C/Co by dividing the depth of Cl calculate retardation. The PHREEQC simulation used
penetration by the corresponding depth for Pb. Results input values of Deff to match the Pb in the pore fluid
are presented in Table 2. The simulated R is 23.6 of the 520-day experiment and only precipitated the
when C/Co is equal to 0.5 and 22.3 for C/Co of 0.1. amount of Pb required to satisfy a simple linear ion
Simulated retardation decreases to about one-half exchange process. Retardation was calculated by com-
these values when C/Co is 0.01, presumably due to parison with the hypothetical penetration profile of a
dispersion introduced by the choice of cell size for the non-reactive solute. Actual measurements indicate
model and other factors increasing the apparent dis- that the clay materials are retaining more Pb than
persion of the advancing pore fluid front. Simulated the simulation predicts.
retardation values near 23 are 22  smaller than the The differences in retained Pb are apparent in Fig.
value (503) reported by Roehl and Czurda (1998). 6, which compares the total quantity of Pb adsorbed by
Differences in R are reflected in differences in the ion exchange under the simulated transport conditions
apparent diffusion coefficients (Dapp), 4.7  10  13 with the actual measurements of Roehl and Czurda
and 1.3  10  11 m2 s  1, respectively. These coef- (1998) after 121 and 520 days. The simulated values
ficients suggest slower rates of Pb transport in the are always lower than the measured ones but are very
experimental situation because more Pb is retained by close to the quantities attributed to the ‘‘exchangeable’’
reaction with the soil. fraction by Roehl and Czurda (1998). Comparing the
solid circles that represent measured values to the
curve drawn through the open circles (Fig. 6) illus-
4. Discussion trates that the simulated values are within 70– 80% of
the measured total after 520 days of reaction. The data
The experiment and the simulation produced for 121 days provide a similar comparison. The
nearly identical results for Deff, the diffusion coeffi- simulations fail to account for (up to 30%) the Pb
cient that accounts for the influence of tortuosity on contained in the ‘‘carbonatic fraction’’. Other sorption
the free-solution aqueous diffusion coefficient. The mechanisms should be used to account for all the
66 R.E. Ferrell et al. / Applied Clay Science 21 (2002) 59–66

tainties associated with the natural environment can


be modelled to evaluate their relative importance.
PHREEQC is a flexible routine that provides ways to
assess the roles of changing clay content, particularly
CEC and exchange ion specificity, on the calculated
element profiles produced by diffusive transport. Spe-
cific adsorption reactions can be included in the model
to account for the retardation of reactive elements.
Modelling is a useful approach for the study of metal
retention by clay liners. However, it must not be used
as a complete substitute for field and laboratory inves-
tigations. PHREEQC results are in generally good
agreement with Deff determined in the laboratory study
Fig. 6. Total quantity of adsorbed Pb predicted by simulations based of Roehl and Czurda (1998) but differences in the
on ion exchange (curves) compared with the data from 121- (open observed and predicted retardation factors result in the
squares) and 520-day (open circles) experiments of Roehl and
more rapid transport of Pb in the model clay liner.
Czurda (1998).

reactions retarding the transport of Pb. In essence, the References


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