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Engineering Geology 60 (2001) 209±221

www.elsevier.nl/locate/enggeo

An investigation into contaminant transport processes through


single-phase cement±bentonite slurry walls
L.K. Philip*
School of Earth Sciences, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK
Accepted for publication 20 April 2000

Abstract
Cement±bentonite walls are commonly used for remediation by containment or pollution prevention, in addition to their use
as a barrier to water ¯ow in more conventional construction. The results from an investigation of an in situ single-phase
cement±bentonite slurry wall are detailed, with particular attention paid to the role of advective and diffusive ¯uxes in
contaminant transport.
The wall under investigation was installed, using standard methods and with a normal mix design, in August 1995 in order to
contain leachates arising from `piggy-backing' of an existing `dilute and disperse' land®ll site. In September 1998, the wall was
investigated during which the top of the wall was exposed at adjacent locations allowing the drilling of three boreholes using
rotary coring techniques. Core recovery and quality were high and samples obtained during coring were retained for testing in
the laboratory.
The material recovered was quite strong and not treatable by conventional soil testing and preparation techniques. In
addition, the material was susceptible to drying upon exposure to the atmosphere, with an accompanying loss of structure.
In spite of this, meaningful laboratory tests were undertaken. Hydraulic conductivity of the samples was measured using
constant ¯ow-rate methods and the relative importance of the diffusive ¯ux was investigated using a variety of simple
techniques. The advective ¯ux was found to be the dominant contaminant transport process. The results of the laboratory
test programme are presented and placed in the context of the long-term performance of cement±bentonite slurry walls. q 2001
Elsevier Science B.V. All rights reserved.
Keywords: Land®lls; Disposal barriers; Permeability; Advection; Diffusion; Breakthrough curves

1. Introduction constituents of these walls are:

Cement±bentonite slurry walls are in common use ² cementitious materials (usually cement and ground
as vertical cut-off barriers to allow the containment of granulated blast furnace slagg (GGBS));
liquids and gases in the ground. Trenches are exca- ² bentonite clay (usually sodium exchanged calcium
vated under cement±bentonite slurry which initially montmorillinite);
supports the trench during construction and later self ² water.
hardens in situ Ð hence the term single-phase. The
It is important that the long-term behaviour of
* Fax: 44-113-2335-259. these walls is understood before heavy reliance is
E-mail address: l.philip@earth.leeds.ac.uk (L.K. Philip). placed upon their long-term integrity as pollution
0013-7952/01/$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0013-795 2(00)00102-2
210 L.K. Philip / Engineering Geology 60 (2001) 209±221

Table 1
Wall constituents, details and age at the site

Site Date of wall installation Natural geology Depth of wall (mbgl) Mix proportions (kg)

Bentonite OPC GGBS Water

Yorkshire August 1995 Glacial clays, sands and gravels 1±6 40 40 150 920

containment barriers. Although a reasonable knowl- 2. Site and ®eldwork


edge base has been built up on the performance of
freshly-mixed samples and laboratory mixes, rela- The wall investigated was situated in Yorkshire,
tively little work has been undertaken to give a UK, and details of the wall and its construction can
realistic insight into the true condition of slurry be found in Table 1. The wall was installed as a reme-
walls in situ (ICE 1999; Jeffris, 1993; Tedd et al., dial measure in 1995 due to the implementation of a
1993; Tedd et al., 1997a,b). In addition, the design new phase of land®lling to be operated under different
requirement of these walls tends to be the attainment licensing conditions. It is therefore possible that the
of a low hydraulic conductivity (k , 1 £ 10 29 m/s) wall was exposed to contamination on either side
and therefore at these low permeabilities the advec- during curing. A sketch section across the installed
tive ¯ux may be less important and the diffusive ¯ux wall can be seen in Fig. 1. The results from the moni-
may play an important or even dominant role in toring wells scattered inside, outside and adjacent to
contaminant transport. Little attention has previously the wall, around the land®ll site, suggest that 3 years
been given to the role of the diffusive ¯ux in these after construction, leakage or contaminant break-
walls. through is not detectable through the walls. Based
It is rare that barrier wall owners will allow the on water levels in the monitoring wells adjacent to
exhumation and/or sampling of the existing walls; the wall, the pressure head across the wall, at the
however, this paper describes a ®eld investigation location investigated, generally varies between 0.8
and follow-up laboratory work of a wall at an active and 1.3 m; however, due to the glacial geology it is
land®ll site. likely that complex perched water tables exist.

Fig. 1. Section through cement±bentonite slurry wall.


L.K. Philip / Engineering Geology 60 (2001) 209±221 211

Table 2
Summary of ®eld work and associated ®ndings

Site Extent Equipment Problems Findings

Yorks Three exposures of top of wall Hand equipment Management Wall seen to be in good
problems due to condition with no
environmental issues oxidation visible
Three boreholes Track mounted Access dif®culties Excellent core recovery a
wireline rotary
rig
a
The wall material became more stony near the base of the hole due to intermixing with the host material.

Fieldwork was undertaken in September 1998 The results are summarised in Table 3. A relationship
when the wall was about 3 years old and a summary between depth and moisture content was not found.
of the work is displayed in Table 2 and Fig. 2. Upon drying the samples collapsed with an associated
Fresh slurry wall material is a rich blue colour due loss of structure, as seen in Fig. 3; however, it was
to the impurities originating from the GGBS. Upon possible to preserve some structure by con®ning the
exposure to air the sulphides in the material oxidise specimens during drying. X-ray diffraction con®rmed
and the material turns beige±white, allowing easy the material to comprise cement minerals, with no
visual assessment of defects, cracks, and zones clays occupying $5% by volume being detected.
which may have desaturated. Any such `oxidation' Scanning electron microscopy indicated that the
zone could be interpreted as a desaturation zone and specimen structure may have large open pore spaces
a breakdown in the long-term integrity may be with a skeleton of cement minerals. At the micro-
implied. In the absence of oxygen, the damaged scopic scale a heterogeneous mix of cement minerals
zones may not be visible. is found whereas on a macroscopic scale the slurry
The wall investigated was found to be in excellent wall material looks homogenous.
condition, with no cracks or defects visible and only a
very thin oxidation layer (,1 mm) encapsulating the
4. Hydraulic conductivity testing
wall.
4.1. Methods

3. Index testing Permeability testing was undertaken in a triaxial


cell using the constant ¯ow-rate method. This is an
A programme of simple laboratory testing was accepted technique that offers several advantages over
undertaken on samples collected during the ®eldwork. more conventional techniques, as described by Aiban

Fig. 2. Schematic of ground investigation at Yorkshire site.


212 L.K. Philip / Engineering Geology 60 (2001) 209±221

Table 3
Summary table of the results of index testing

Wall Moisture Bulk density mean (mg/m 3) Dry density (mg/m 3)


content (%)
min/max/
mean

Yorkshire site 212/307/249 1.23 0.35

and Znidarcic (1989). One such advantage is that it is Tests were routinely undertaken with cell pressures of
easier to control the small ¯ow rates rather than 600 kPa and back pressures of 500 kPa, and were
measure them (as required in a constant head test) computer logged for ease of determination of achieve-
and although the head does vary over the test, it ment of steady-state conditions. Hydraulic gradient
increases in a controlled way until steady state is averaged about 27 and varied between 3 and 70. Typi-
achieved at a constant head. The experimental set- cal ¯ow rates were between 0.001 and 0.01 ml/min,
up, seen in Fig. 4, has been well used at the University with the tests taking anything from 20 min to 2 days.
of Leeds and found to be ideal, with a main advantage
being the ¯exibility in test regimes and the ease of 4.2. Results
diagnosis of errors, equipment failure and leaks. In
addition, the tests are relatively short-term, thereby The results from the permeability testing can be
minimising the effects due to biological growths and seen in Figs. 5±8 and are summarised in Table 4.
the effects of temperature variation. The permeability varied and, except for the top of
Test samples comprised 50 mm diameter samples BH2, gave results of the order 10 28 to 10 210 m/s.
taken from the rotary cores obtained in the ®eld. The top of the wall had a slightly larger permeability,
Samples were obtained by laboratory rotary coring thought to be associated with leachate degradation of
techniques and were fully saturated prior to testing. the wall (evidenced from chemical testing), but no

Fig. 3. Total collapse of samples upon drying.


L.K. Philip / Engineering Geology 60 (2001) 209±221 213

Fig. 4. Equipment con®guration for permeability in triaxial cell experiments.

other conclusive trend in permeability with depth date the test regime as, within the range adopted by
was observed at lower depths. No leachate degrada- the testing programme, hydraulic conductivity was
tion of the top of the wall was visible on site although generally independent and insensitive to changes or
some loss of strength was apparent (but not increase in the value of the hydraulic gradient.
quanti®ed) when handling these specimens in the Although all the tests were undertaken at initial
laboratory. effective con®ning pressures of 100 kPa, and most
In addition, to ascertain the effect of hydraulic within similar hydraulic gradients, the effect of
gradient upon hydraulic conductivity a number of increasing effective stress was investigated and the
samples were tested at a variety of gradients with results can be seen in Fig. 8. At large effective stresses
the results shown in Figs. 6 and 7. These results vali- inelastic deformation takes place and the specimen

Fig. 5. Variation in k with depth.


214 L.K. Philip / Engineering Geology 60 (2001) 209±221

Fig. 6. Effect of hydraulic gradient on k values, BH2.

was quite sensitive to changes in effective stress; tered for geological materials (Neuzil, 1994). The
however, at lower values of effective stress elastic maximum effective con®ning pressure that a wall
deformation takes place and changes in hydraulic will be under in situ is about 200 kPa. Further work
conductivity are not signi®cant. While there is a on the changes in k in relation to the timing of the
large overall change in the permeability due to application of con®ning stress during curing is
con®ning stress, it is not outside the range encoun- reported in Manassero et al. (1995).

Fig. 7. Effect of hydraulic gradient on k values, BH3.


L.K. Philip / Engineering Geology 60 (2001) 209±221 215

Fig. 8. Variation in k with effective stress.

5. Diffusion testing tortuosity factor, De the effective diffusion coef®cient


through soil/rock, u the volumetric water content, and
5.1. Background to theory t the tortuosity.
For transient diffusion, Fick's second law is used,
Diffusion is the movement of contaminant due to a which describes the rate of change in concentration
chemical potential gradient. Steady-state diffusion is over time with distance for conservative (non-retar-
governed by Fick's ®rst law and, for ¯ow in a porous dant) ions,
media,
dc d2 c
dc ˆ Dp 2
f ˆ 2Dp dt dx
dx
where D p (retarded coef®cient of hydrodynamic
and
dispersion) ˆ De and therefore the tortuosity can be
Dp ˆ vT D0 ˆ uDe ; De ˆ tD0 ; vT ˆ tu calculated from De ˆ tD0 :
Further discussion of diffusion is presented by
where Dp is the porous media diffusion coef®cient, D0 Rowe et al. (1995).
the free solution diffusion coef®cient, v T the complex

Table 4 5.2. Laboratory testing


Permeability test results (in obtaining these values, the two high
values at the top of BH2 have been ignored Ð this is because 5.2.1. Methods
those results are thought to be due to leachate degradation of the Two types of simple diffusion experiments were
material) undertaken in an attempt to quantify the diffusion
Values for all tests k (m/s)
parameters and the relative importance of diffusion
as a means of contaminant transport through these
Maximum 2.6 £ 10 28 walls. A double reservoir diffusion cell was designed
Mean 5.9 £ 10 29 and constructed (see Fig. 9), and a double reservoir
Median 3.1 £ 10 29
tank with sample tubes used (see Fig. 10). In
Minimum 1.3 £ 10 210
both types of test, the chloride ion Cl 2 (from sodium
216 L.K. Philip / Engineering Geology 60 (2001) 209±221

Fig. 9. Double reservoir diffusion cell.

chloride) was chosen as the diffusing ion. Initial reser- generally, ,0.008 although one test yielded a higher
voir concentrations were around 16,100 mg/l Cl 2 and result of 0.013. Some interfacial partitioning, referred
10,500 mg/l Na 1 for the diffusion cell and 10,700 mg/ to by Rowe et al. (1995) and described in greater
l Cl 2 and 6800 mg/l Na 1 for the diffusion tank. The detail by Kemper and van Schaik (1966), was found
diffusion experiments were conducted at a constant and so both modelling and mass balance techniques,
temperature of 228C ^ 1. where applicable, were used in deriving tortuosity.
The exclusion of leakage pathways was the main During interfacial partitioning, a sharp drop in
problem encountered in devising the experimental set- concentration gradient across both reservoir±soil
up and this was due to the nature of the material, interfaces, especially the high-concentration side,
which was strong enough to core like a rock but not was observed. This effectively produces a very low
strong enough to achieve completely perfect cores of diffusion coef®cient and a large concentration gradi-
consistent size. Also, unlike clay soils, the material ent in a very thin interfacial layer. In the modelling, in
was too strong to be moulded into place. Low-pres- order to achieve good-®t curves to the theoretical and
sure seals, o-rings and membranes or non-reactive actual data, the initial concentrations have been varied
putty were used to prevent leakage around the sides in order to model the effects of interfacial partitioning.
of the sample. Theoretical and actual data curves had a good ®t and
At the termination of each experiment, after around there was reasonable agreement in the tortuosity
1 month, the samples were divided into sub-samples factors obtained from the Cl 2 ion and the Na 1 ion,
along the length, and pore ¯uids extracted. The reser- as can be seen in Figs. 11 and 12. This indicates that
voir and pore ¯uids were analysed for chloride and the Na 1 ions are not being retarded when compared
sodium ion using ion chromatography (IC). with the Cl 2 ions, which is probably due to the
composition nature of the original mix which was
5.2.2. Results rich in Na±bentonite, and therefore most of the sites
Analysis of the results indicates the tortuosity to be, for Na 1 ions were presumably already occupied.
The values of tortuosity obtained are very low,
compared with the clayey barriers; however, any
error in the tests such as leakage paths, higher than
anticipated background ion counts, etc. would tend to
increase the values of tortuosity obtained. Such a low
tortuosity would imply extremely slow diffusion
times. Although a conservative ion was used in
these experiments, it is possible that the slurry wall
material has considerable retardation potential,
through ion exchange with calcium silica hydrate
Fig. 10. Double reservoir tank. (CSH) or cement, minerals and ettringite (Gougar
L.K. Philip / Engineering Geology 60 (2001) 209±221 217

Fig. 11. Comparison of theoretical and experimental results: Cl 2.

et al., 1996), and that the results were affected by one or two horizons with no pattern emerging. A
retardation Ð so producing `falsely' low values for possible trend of decreasing lithium concentration
tortuosity. with depth was identi®ed but it is thought to be not
conclusive. Both Ca and Sr show a possible but incon-
5.3. Field pro®les clusive depletion at shallow depths. Most of the varia-
tions picked up are thought to be due to micro-scale
Pore ¯uids were analysed using IC and inductively variations in wall chemistry, particularly due to the
coupled plasma (ICP) techniques to see if a contami- metals present in the GGBS.
nant plume due to leachate presence could be Using IC, an advection/diffusion front was success-
identi®ed. fully identi®ed for chloride ion (see Fig. 13) with
ICP results were fairly inconclusive. Several ions signi®cant Cl 2 concentrations at shallow depth drop-
(Ba, Al, K, As, Na) showed some variation with no ping off to virtually zero deeper in the wall found.
depth pattern emerging. Several ions (Zn, Pb, Cd, Cr) Due to the inherent unknowns, the assessment of
were undetected while some (Mn, Ni, Fe, Mg, Cu) transport parameters from the ®eld pro®les is dif®cult
showed very low detectable concentrations at just and therefore not attempted here.
218 L.K. Philip / Engineering Geology 60 (2001) 209±221

Fig. 12. Comparison of theoretical and experimental results: Na 1.

6. Modelling from the ®eld site investigated where possible


contamination from leachate was found after 3 years
Predictive diffusion breakthrough curves for the (see Fig. 13).
worst case tortuosity 0.013, assuming a steady From the models of advective and diffusive
leachate concentration and conservative (non-retar- transport it is clear that for this wall the advective
dant) ions …D0 ˆ 2:03 £ 1029 m2 =s†; have been gener- ¯ux is dominant in contaminant transport, even if
ated (see Fig. 14). For a 600 mm thick slurry wall it the higher values of k from the laboratory testing are
will be 20 years before breakthrough at 0.1% of the disregarded as being unrepresentative of the wall as a
source concentration and 80 years before break- whole.
through at 10% of the source concentration. All the breakthrough times and the modelling
Predictions for advective breakthrough have also assume that the barrier retains its chemical integrity
been made using the permeability results given in with time, which is a precondition outside the scope
Table 4, assuming a porosity of 0.75 and a hydraulic of this work but has been investigated by others
gradient of 1. The breakthrough times can be seen in (Ahtchi-Ali and Casper, 1997; Garvin and Hayes,
Fig. 15. The results given are supported by evidence 1998).
L.K. Philip / Engineering Geology 60 (2001) 209±221 219

Fig. 13. Chloride concentration with depth.

7. Summary of the ®ndings and discussion of construction, an advective/diffusive pro®le was


seen to be present within the boreholes in the
7.1. Advection versus diffusion middle of the wall extending 700 mm down into
the wall. It is unclear why contamination was not
The advective ¯ux has been shown as the domi- present for the full depth of the wall and, by
nant process for contaminant transport across the means of explanation, it is thought that: (a)
slurry wall. At the Yorkshire site, within 3 years there were perched unconnected leachate tables

Fig. 14. Predictor plot for diffusive transport.


220 L.K. Philip / Engineering Geology 60 (2001) 209±221

Fig. 15. Breakthrough times for advective transport.

inside the wall; and/or (b) there was a vertical Acknowledgements


leachate ¯ow due to downward permeation from
the cap/wall junction. This paper reports part of a wider programme of
research into the long-term performance of single-
phase cement±bentonite slurry walls. The programme
7.2. Long-term performance was supported by EPSRC through grant GR/L90828
and they are thanked for their support. Wastewise, in
The wall looked visually excellent when exposed particular Simon Jones, is thanked for their collabora-
and recovered in the ®eld but the k values and asso- tion, and in addition a number of people at the Univer-
ciated breakthrough times were disappointingly high. sity of Leeds are also thanked for their advice and/or
It has been found (Tedd et al., 1997a,b) that with this chemical testing: Dr A. Bolton, Dr J. West, Dr R.
material a reduction in permeabilities of an order of Mortimer, and Mr K. Handley. The author thanks
magnitude can be seen during the long-term tests. the reviewers Dr P. Tedd and Dr S. Jeffris for their
These were not, however, undertaken as it was felt time spent and their constructive remarks.
that more information could be yielded from a large
number of short-term tests that are similar in nature to
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