Construction and Building Materials 13 1999.

329 341

The chemical compatibility of cement bentonite cut-off wall material

Stephen L. GarvinU , Carolyn S. Hayles
Building Research Establishment, Scottish Laboratory, Kel in Road, East Kilbride G75 0RZ, UK Received 20 May 1998; received in revised form 4 May 1999; accepted 9 May 1999

Abstract Containment techniques are amongst the most common methods of remediating land contaminated by previous industrial use. An important part of the containment process is the placing of vertical in-ground barriers to minimise the movement of contamination from site. Self-hardening slurry trench cut-off walls of cement bentonite are barriers that are increasingly being used in the United Kingdom. The use of cement bentonite slurry trench cut-off walls, particularly in highly aggressive environments, raises concerns over durability and long-term performance. The relatively recent use of such barriers means that there is little information on their long-term performance. This paper describes research being undertaken to investigate the properties of cement bentonite cut-off walls and to examine potential durability problems. Laboratory immersion tests have been used to assess the chemical resistance of typical cement bentonite mixes containing ordinary Portland cement, ground granulated blast-furnace slag and pulverised fuel ash. These mixes showed varying degrees of resistance to chemical attack with pulverised fuel ash mixes more resistant than those with ground granulated blast-furnace slag. The advantages and limitations of such tests are discussed. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Cut-off wall; Cement bentonite; PC

1. Introduction It is uncertain as to how much contaminated land there is in the UK. The House of Commons Select Committee estimated in 1990 that there are between 50 000 and 100 000 contaminated sites. Contaminated land may pose threats to human health, the natural environment and buildings. It is wrong to categorise all sites of a certain kind as being contaminated, but typical contaminated sites include domestic and industrial landll sites where leachate and gases may be generated, and land previously used for industrial purposes. Contamination may spread out from these sites
U

Corresponding author. Tel.: q44-1355-233-001; fax: q44-1355241-895. E-mail address: garvins@bre.co.uk S.L. Garvin.

and affect groundwater, surface water and neighbouring land and immediate action is required to remediate the site. On some sites the contamination may not pose a threat in its existing use, but redevelopment may be delayed until remediation occurs. The reuse of contaminated land is a valuable contribution to urban regeneration, and the number of contaminated sites used for construction is expected to rise. The basic remediation options for such sites are containment, treatment and excavation and removal to landll. The principal encapsulation or containment methods involve using appropriate cover or cut-off wall systems w1x. It is recognised that encapsulation does not necessarily result in a long-term solution as the contamination itself still exists, but encapsulation generally offers both a more cost-effective solution and one which uses

0950-0618r99r$ - see front matter 1999 Elsevier Science Ltd. All rights reserved. PII: S 0 9 5 0 - 0 6 1 8 9 9 . 0 0 0 2 4 - 0

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S.L. Gar in, C.S. Hayles r Construction and Building Materials 13 (1999) 329 341

established engineering techniques of construction; most importantly it avoids disturbing the contaminated area. A review of containment and control measures has recently been produced in the UK w2,3x. One of the most common forms of vertical barrier in the UK is the cement bentonite slurry trench cut-off wall, an engineering-based remediation method which represents a relatively low-cost solution for contaminated land sites w4x. These systems, consisting of selfhardening cement bentonite, were initially developed for water exclusion or as a hydraulic cut-off, for example, in dam foundations. However, they are now more commonly used as barriers to control lateral migration of contaminants from former industrial sites and landll sites. In situations where barriers are built adjacent to landll sites and control of gas migration is required, geomembranes, usually high-density polyethylene HDPE., are frequently incorporated into the barrier. There is concern that leachates generated from some old industrial sites, such as chemical and gasworks sites, or toxic wastes disposed in shallow areas of a site, may have an adverse effect on the performance of a cement bentonite barrier. There are potentially several physio-chemical mechanisms by which contaminants in the groundwater can affect the swelling of the bentonite and thus the performance of the slurry. In addition, and perhaps more importantly, the contaminants may attack the set material and affect long-term durability and performance. The aims of the research were as follows:

terials have been commonly specied and used:

bentonite, normally sodium exchanged, described as CE civil engineering. grade; Portland cement PC.; partial PC replacement materials; this is mainly ground granulated blast-furnace slag ggbs., but pulverised fuel ash pfa. has also been used and microsilica has potential; and admixtures, these include set retarders and dispersants.

to investigate the fundamental chemical compatibility of cement bentonite with common contaminants through tests on laboratory samples; and to improve the understanding of the materials as a contribution to validating their use and improving specication.

The results detailed in this paper are based on tests on mixes based on Portland cement and pulverised fuel ash. While it is more common to specify mixes with Portland cement and blast-furnace slag, these mixes were the subject of previous papers w4,5x. The mixes of Portland cement and pulverised fuel ash also showed potentially better chemical compatibility in previous tests and a more thorough study was required.

Bentonite is a clay composed largely of dioctahedral smectites, usually montmorillonite w6x. The exchangeable cations are calcium, sodium and to a lesser extent aluminium., giving rise to the classication of calcium or sodium bentonite. In the UK, the most common bentonite used is a civil engineering grade sodiumexchanged bentonite; this is calcium bentonite that has been treated with sodium carbonate and is otherwise known as sodium-activated bentonite. Sodium-exchanged bentonite has an outstanding ability to swell on uptake of water, expanding to between 10 and 15 times its original volume w7x, which gives rise to complete dissociation of the smectite crystals. Other important aspect of bentonite suspensions are that it has a high sorptive capacity, a thixotropic nature and a high dispersibility w8x. The microstructure of hydrated bentonite suspensions is a connected and porous network of anisometric particles which assist the high sorptive capacity. The use of ggbs reduces the overall cementitious quantity required to achieve a given permeability and normal replacement levels are 70 80%. Alternatively, pfa has been used as a partial replacement material. Replacement levels between 10 and 30% are normal. Above 30% the resulting hardened slurry may be too weak for this purpose w9x. Typical mix proportions w10,11x used in barriers for various purposes lie in the range:
Typical mix proportions Bentonite Cementitious material Water PCrggbs PCrpfa PC 30 60 kg 100 350 kg 1000 kg 90 200 kg 150 350 kg 90 200 kg

Cementitious component

2. Cementbentonite slurry trench cut-off walls 2.1. Materials and construction 2.1.1. Material properties The range of materials used for slurry trench cut-off walls in the UK is not extensive. The following ma-

2.1.2. Mixing procedure Mixing is generally carried out on site with the cement bentonite slurry later pumped from the mixing plant to the trench. The basic mixing procedures can be briey summarised as follows: 1. mix the bentonite and water;

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2. leave to hydrate for a period between 4 and 24 h; 3. add the cementitious component, in a dry powder form or as a slurry; and 4. pump the material to the trench and allow to set; insert membrane prior to setting if specied.

2.1.3. Slurry trenches The majority of cement bentonite slurry trench cutoff walls for containment purposes in the UK are formed using the single-phase method where the trench is typically 0.6 m wide and is excavated under a selfhardening slurry. The slurry is left in the trench to set and harden over a period of 2 3 days. Excavation of shallower trenches, up to 12 m depth, in relatively at ground, is usually achieved with a backactor. For deeper trenches and difcult ground conditions, grabs and cutters are used and a double-phase method is normally used. If continuous excavation through the slurry is likely to cause problems then the cement bentonite slurry is used to replace a bentonite excavation slurry. If a geomembrane is to be inserted, retarders are normally used to delay the setting time. 2.2. Specication Specication of slurry trench cut-off walls is normally made on the basis of performance as opposed to prescription. There is, at present, insufcient published data for speciers to be more prescriptive. A specication for a barrier would, typically, include the following:

perceived need for a deformable cut-off, which is less likely to crack and leak, particularly if ground movements are envisaged. A value of 5% in a drained triaxial test is often quoted, however, this strain criterion is difcult to achieve with the 10y9 mrs permeability requirement. This is particularly so where compliance testing is carried out at 28 days. Also the 5% strain can generally only be achieved, if at all, by testing at effective conning stresses much higher than those which exist in situ; Strength: Where unconned compressive strengths have been specied, the values have varied considerably, between 100 and 1000 kPa. Sometimes a minimum or maximum value is specied and sometimes a range of values. There is little agreement on what is required. Increasing the cementitious content from 100 kg to 350 kg can increase strength by a factor of 4 to 5, but at the higher cement contents the mix can be excessively thick and produce a hardened slurry that is strong but brittle. At the lower cement contents the mix can be weak. Such mixes also contain more water and so are liable to greater drying shrinkage and cracking if left exposed before capping. At cementitious contents less than 90 kg set is unlikely to occur.

specication of uid properties; specication of hardened properties; durability requirements; quality control on site during construction; and specication of materials as supplied.

2.2.1. Performance specication The properties of the hardened slurry and durability are the most important factors that inuence long-term performance.

2.2.2. Effect of materials on specication The use of ggbs as a replacement material can produce higher early strengths and lower permeabilities than straight PC mixes. However, the hydration characteristics of PCrggbs mixes can pose difculties in meeting both the permeability and strain specication. The strength development is initially more rapid and continues for longer than for neat PC mixes w12x, so mixes containing ggbs which have a permeability of 10y9 mrs at 28 days will become more brittle and would be unlikely to have a strain at failure greater than 5% at the same time. If compliance testing is necessary at 28 days for contractual requirements, specifying a permeability of 10y8 mrs would produce a less brittle mix which is more capable of achieving the required strain at failure, and which would eventually reach a permeability of the order of 10y9 mrs w10x. 2.3. Chemical compatiblilty of cement bentonite The chemical compatibility of cement bentonite depends on the behaviour of the cement binder and the clay when exposed to a particular contaminant or mixture of contaminants w13x. The slurry may be susceptible to attack from chemicals which would normally attack either hydrated cement or bentonite, and there is a need to identify the contaminants most likely to reduce the effectiveness of the slurry material.

Permeability: Normally specied as less than 10y9 mrs drained triaxial cell test.. The use of ggbs in the slurry is normally necessary in order to achieve this permeability. Other cementitious materials may not give as low a permeability w2x. These tests are carried out at 28 days andror 90 days. The use of bentonite contents above 40 kg gives a marked reduction in permeability and also increases strength. Above 60 kg the slurry becomes thick and difcult to mix and pump w10x; Strain at failure: Generally specied because of the

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2.3.1. Compatibility of the fresh slurry There is substantial literature on clay-chemical interactions, but less on the physico-chemical behaviour of bentonite and specically sodium-exchanged bentonite used in cut-off walls. However, it is well established that bentonite consists of a connected and porous network of anisometric particles w8x. The connectivity and isotropy of bentonite is achieved by the exibility of the clay sheets and its lenticular porosity as a result of this stacking. These factors produce the high swelling characteristics and low permeability required to prevent seepage of contaminants. The loss of water, increased permeability, and alteration of the microstructure of the cement bentonite slurries are believed to be the result of calcium ion concentrations and high pH solutions w8x. Rheological properties of the cement bentonite appear to be controlled by a rise in pH, which is associated with cement hydration reactions. Viscosity is the single most important property controlling the characteristics of the cement bentonite slurry, and it is believed that high pH values thicken bentonite suspensions w8,14x. Sodium-exchanged bentonite will readily exchange its sodium ions for other ions such as calcium and aluminium, creating a material that does not have the capacity to swell to the same extent as the sodium-exchanged bentonite, but nearer to that of natural sodium bentonite w7x. The process of calcium-induced aggregation is a major factor which controls the unwanted increase of permeability and water loss. The swelling of sodium-exchanged bentonite can also be inhibited by the presence of other sodium salts. The net effect of these chemical reactions will be a fall in the swelling capacity of the bentonite and thus a reduction in the effectiveness of the bentonite as a sealant w7x. 2.3.2. Compatibility of the hardened slurry Investigation of the effect of contaminants on hardened cement bentonite has been addressed by previous workers using several methods. The principal four methods are as follows:

Contaminants which are considered likely to affect the integrity of cement bentonite barriers include inorganic and organic acids, magnesium and ammonium salts and sulphates w18x. A description of the principal mechanisms of attack follows.

Acids react with the calcium in the cement hydrates to degrade the binder. The rate of reaction is dependent on the solubility of the reaction product, which if low can inhibit further reaction. Magnesium and ammonium salts attack the cement paste fraction. Ion-exchange transforms insoluble calcium in the hardened cement paste into soluble calcium salts which are subsequently leached out of the material. Sulphates react with the hardened cement paste. The reaction products which form a greater olume than the reactants. In unconned samples this leads to disintegration by expansion and cracking. Phenol weak acid. and other organic solutions have a negligible effect on cement bentonite. Some organic molecules (e.g. aniline and ammonium chloride) were found to cause disruption to the structure and porosity of cement bentonite w19x.

mixing the material with appropriate volumes of contaminants and analysing reaction products w15,16x; immersing specimens in solutions of single or combined contaminants w15 17x; permeating the material with contaminants in a triaxial cell with a hydraulic head and conning pressure w13x; and diffusion tests w16x.

These different test conditions give different information on the materials behaviour. Therefore, the test regime used should be considered when analysing, interpreting and applying results.

The type of cement and proportions of replacement materials are thought to affect the chemical resistance. Some authors have suggested that partial replacement of some PC by ggbs is benecial to sulphate resistance and also has benets in lowering the permeability of the material w20 22x. Between 60 and 80% replacement has been described as the desired replacement level. Alternatively, pfa can be used to replace some of the PC and this may give even better resistance to sulphate attack than ggbs. The importance of the C 3 A content in PC has been described elsewhere w20,23x and it has been recommended that at sulphate levels in the groundwater or soil of between 150 and 1500 mgrl, the C 3 A content should be no greater than 8%. Above a sulphate level of 1500 mgrl, the C 3 A content should be no greater than 5%. However, due to the lack of data in these publications it was not certain whether these conclusions were the result of testing or were adapted from concrete technology. The form of chemical attack may not always lead to a diminution of the physical properties of the material. Pore blocking may occur leading to a reduction of the permeability. An important function of a cement bentonite barrier would be to remove contaminants by attenuation mechanisms. This is primarily a function of the bentonite fraction which readily exchanges cations and can bind up heavy metals and other contaminants. When assessing the effects of reactive chemicals it is important to realise that a major source of damage may be the dissolution of the cement bentonite without any

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specic chemical reaction. It has been argued that if aggressive chemicals are present, the cement will be attacked rather than the relatively inert bentonite w24x. Thus, high bentonite concentrations should be used on aggressive sites. The lower permeability of the higher bentonite content mix will also help to regulate the rate of attack on the cement by the contaminants. Other work indicated that attack on plastic concrete, made from cement bentonite with aggregate, may be more severe than on a cement bentonite cut-off barrier without aggregate w22,25x. 2.3.3. Pre ious BRE work Previous work undertaken by BRE has included tests on the chemical compatibility of cement bentonite with contaminants that are commonly found on old industrial sites, and assessing the physical properties of cement bentonite both in the ground and using samples retrieved from site. Previous laboratory work, using immersion tests, has highlighted problems associated with the chemical compatibility of cement bentonite mixes with common in-ground contaminants. This initial work w4,5x included a variety of mixes and a range in the mix proportions including a number of mixes using PCrggbs mixes commonly used on site, and PC and PCrpfa mixes not typical of those currently used in the UK. Immersion tests at BRE were undertaken on samples in solutions of both single and mixed contaminants. These tests included a set of cement bentonite mixes immersed in different sulphate solutions. The reference solution in the sulphate experiments was 2y . sodium sulphate SO4 , 2500 mgrl; class 3 sulphate conditions as dened in Digest 363 w4,26,27x. It was assumed that the sodium ion itself would have a nil or negligible effect on the material. The concentration of sulphate ion in solution ranged from 1000 to 5000 mgrl. Some of these solutions were found to be particularly aggressive causing degradation of all the cement bentonite mixes. The degree of attack was linked to the concentration of the sulphate ion. At lower concentrations, up to 2000 mgrl, only the weaker mixes or those containing a signicant proportion of ggbs were at risk of degradation. The poor performance of ggbs mixes was in contrast to the improved performance that was expected by other workers. At concentrations above 2500 mgrl the chemical resistance of all mixes decreased and this was seen most markedly at 3500 mgrl and above. The aggressiveness of the solution depended not only on the sulphate concentration but also on the counter ion present. The relative aggressiveness was q 2q Mg 2q) NHq 3 ) Na ) Ca . A combination of sulphate and acid pH s 2.5., gave a greater degree of deterioration than sulphate in isolation.

The overall performance of the PCrggbs bentonite mixes in sulphate solutions was poor and immersion tests showed that these more commonly used cement bentonite mixes were not chemically compatible with sulphates, acids and magnesium salts; the performance of a limited number of PCrpfa bentonite mixes was better than that of the PCr ggbs bentonite mixes. The proportion of bentonite present made a negligible difference to chemical compatibility results.

3. Experimental The current laboratory test programme was developed with the aim of investigating the relative chemical resistance of a number of cement bentonite mixes, specically mixes with cementitious material of PCrpfa. As hardened cement bentonite has a much lower strength than concrete and most building mortars, it has at least as much, if not more, in common with clay than concrete. Normal methods of assessing the durability of cement-based materials, such as measuring the compressive strength after immersion could not be directly employed. Instead changes in weight, length and physical appearance were monitored. Immersion tests were chosen to investigate the chemical compatibility of cement bentonite for the following reasons:

they can provide a simple and cost effective way of assessing deleterious effects of contaminants on a range of different mixes; they provide the worst case conditions for chemical attack on cement bentonite and if the material performs adequately well in this test then it can be assumed that it will perform satisfactorily well in the contaminated ground; and immersion tests do not, however, represent realistic environment. The availability of solution phase contaminants that could react with the cement bentonite is much greater than in the ground. In addition, the material is free to expand, crack or contract on chemical attack.

Conned tests have been used to monitor the effects of sulphate solutions on the material in an environment in which the material could not freely expand. 3.1. The mixes A number of cement bentonite mixes were made up under laboratory conditions. These mixes are shown in Table 1 and the mix proportions are expressed as

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S.L. Gar in, C.S. Hayles r Construction and Building Materials 13 (1999) 329 341 Table 2 Chemical analysis of PC and ggbs Oxide pfa %. ggbs %. PC %. Bogue equivalent %. C3 S 52 C2 S 20 C3 A 10 C4 AF 8 CS2 5

Table 1 Mix proportions used in test programme per 1000 l water a Mix no. Bentonite ggbs nra nra nra 40 nra nra nra nra pfa PC Total cement 120 200 200 200 150 150 300 300

1A 2A 3A 4A 1B 2B 3B 4B
a

40 40 40 40 40 40 40 40

36 60 nra 100 37.5 60 75 120

84 140 200 60 112.5 90 225 180

All results given in kilograms.

weights of each material per 1000 kg of water. The chemical analyses of the PC, the ggbs and the pfa used are shown in Table 2. 3.2. Preparation In these tests the quantity of material used to produce the samples in the laboratory was one tenth of the

CaO SiO2 Al2 O3 Fe2 O3 NaO2 MgO K2 O SO3 Mn2 O3 LOI Insolubles Free CaO

1.88 49.41 24.21 13.99 0.57 1.62 3.21 0.76 0.07 2.89

42.78 33.09 12.59 0.4 0.21 7.59 0.38

63.57 22.08 5.15 3.55 0.22 2.4 0.7 3.12

0.4 0.07 0

total mix proportions. The procedure for mixing and curing the slurry was as follows: 1. mix all the sodium exchanged bentonite with all the water for 5 min using a power tool with grout mixer attachment;

Fig. 1. Samples used in immersion tests examples..

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2. leave the bentonite mix to hydrate for 24 " 1 h at 20 " 5C; 3. blend the PC and replacement material either ggbs, pfa or both, see Table 1.; 4. mix in the cementitious material as a dry mix to the hydrated bentonite, mixing time of 5 min; 5. check the quality of the mix, i.e. it was homogeneous and all solids had been broken down by mixing the slurry was mixed further, for 2 min, if necessary .; and 6. pour the fresh samples of the cement bentonite into sample tubes for experimentation.

3.3. Experimental methods 3.3.1. Immersion tests To prepare samples for the immersion tests, the

slurry was poured into moulds sealable sample tubes 100 mm in diameter and 350 mm in length. and allowed to set. After 28 days the hardened material was demoulded and cured under water until the immersion test. The samples were then cut into cores, using a masonry saw, from a cast cylinder of material Fig. 1.. Samples of each mix were then immersed in solutions of potentially aggressive chemicals for a maximum period of 6 months. The solutions were changed on a monthly basis for the duration of the test. The visual condition of each sample was recorded monthly and changes in weight were recorded. Measurement of weights were taken after allowing the sample to drain but not to dry to the touch, as this may have caused oxidation and drying shrinkage and would thus have adversely affected performance. The assessment of the performance of each mix in each solution was derived from a ranking procedure which was previously developed w4,5x. This ranking procedure relies on visual observations and measurement of weight changes. At the end of the 6-month immersion period a ranking was given dependent on performance. A summary of the criteria follows:
Very Poor VP. Sample destroyed within rst month of immersion. Weight changes after 1 month if sample still existed. were generally "50% Sample had a very low resistance to chemical attack and lasted less than half the experimental period. Visual damage was evident. Weight changes over this period were "50% Sample had some resistance to chemical attack. In general sample survived the duration of the experiment. More visual attack was apparent and weight changes were "50% ) x - "15% Sample was resistant to chemical attack with little visual evidence and weight changes of "15% of original weight Attack was at worse marginal during the experimental period. Weight changes were "5%

Poor P.

Moderate M.

Good G.

Very Good VG.

Fig. 2. Conned attack tests set-up.

3.3.2. Conned contaminant attack Conned tests involved casting cement bentonite into 100-mm diameter plastic pipes and providing connement around the material, as shown in Fig. 2. A strong sulphate solution 4500 mgrl. was then placed in contact with the material through a permeable sand layer. The solution was in direct contact with the material and could diffuse into it. Outow was allowed from the bottom of the column. Due to the relatively small hydraulic head, chemical diffusion from the solution into the material was likely to be as important as advection in introducing solution to the material. Sidewall leakage was minimised by allowing the material to

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S.L. Gar in, C.S. Hayles r Construction and Building Materials 13 (1999) 329 341 Table 3 Results of immersion tests by ranking Mix no. 1A 2A 3A 4A 1B 2B 3B 4B A VP VP M G VP P G VP B VP VP P VP VP VP P P C VP M P VP P P G G D VP M VP G P P VP G E M M M M M P G G G VP VP VP VP VP P P

set within the plastic pipe and applying a thin bead of sealant, capable of setting under high humidity, between the cement bentonite and the pipe. The type of test is more representative of the conditions found in the ground, where the cement bentonite experiences a conning pressure, than the immersion tests. However, the conning pressure in the test would be much lower than experienced in the ground. Only mixes 1A 4A were tested in this manner. The condition of this conned material was assessed after 3, 6 and 12 months in three ways:

visual assessment: observation of cracking, softening or discolouration of the material; chemical proling: chemical analysis for SO4 content; and SEM analysis: microscopic investigation of reaction products.

3.4. The solutions Samples were immersed in a number of solutions which included the following common types of contamination:

2y x Solution A: sodium sulphate, wSO4 s 4200 mgrl; 2y x Solution B: sodium sulphate, wSO4 s 4200 mgrl pH s 2.; 2y x Solution C: sodium sulphate, wSO4 s 1000 mgrl; 2y x Solution D: magnesium sulphate, wSO4 s 1000 mgrl; Solution E: phenol s 10 000 mgrl; and Solution F: sulphuric acid pH s 2..

Solution C: sodium sulphate (1000 mg r l; pH G 7) This solution caused deterioration by expansive attack, particularly those with a low cement content. Those samples with higher pfa content proved more resistant than neat PC mixes. However, the PCrggbsrpfa mix was the most resistant to this solution. Solution D: magnesium sulphate (1000 mg r l; pH G 7) This solution caused deterioration to all samples tested, particularly those with lower pfa contents. Results were similar to those for Solution C. Solution E: phenol (10 000 mg r l) Deterioration in phenol solution was by discolouration and softening, but not by extensive cracking and disintegration. However, all the mixes were resistant to chemical attack by phenol. Solution F: sulphuric acid (pH s 2) Rapid deterioration was observed for all samples tested. All mixes showed little resistance to the strong acid conditions and were destroyed within 2 3 months.

4. Results 4.1. Immersion tests Each mix of cement bentonite performed differently in the solutions. The results are detailed in Table 3 using the ranking procedure detailed above. The following observations were made:

4.2. Conned tests 4.2.1. Visual assessment Two 100-mm columns of each mix were examined after 3, 6 and 12 months under the sulphate solution. Photographs showing the condition of the materials from the columns are shown in Figs. 3 5. In all cases the cement bentonite samples appeared to be in good condition. In some cases it can be seen that the contact surface showed some discolouration and was a dark brown colour see Fig. 6.. This may be due to oxidation, leaching out of calcium hydroxide or chemical attack; or indeed a combination of these factors.

Solution A: sodium sulphate (4200 mg r l; pH G 7) Deterioration was observed for all samples tested, particularly those with a low PCrpfa content. Those PCrpfa mixes with highest PC concentrations were most resistant. Solution B: sodium sulphate (4200 mg r l; pH s 2) Rapid deterioration was observed for all samples. The PCrggbsrpfa mix had very poor resistance. PCrpfa samples with high cement content were slightly more resistant.

3 months: no visible signs of attack on any of the materials, mixes 1A 4A. 6 months: the contact surface of mixes 1A 3A had softened slightly due to contact with the strong sulphate solution.

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Fig. 3. Conned samples, mix 1A, after 3 months.

Fig. 4. Conned samples, mix 3A, after 6 months.

12 months: similar to 6 months except accelerated deterioration of mix 3A compared with mixes 1A and 2A. Mix 4A appeared very resistant to chemical attack with no visible signs of softening or cracking.

4.2.2. Chemical diffusion Samples were taken from 10 mm, 25 mm, 50 mm and 100 mm depths from the contact surface . for chemical analysis and 10 mm, 50 mm depths for scanning electron microscopy SEM. analysis. The chemical analysis was a determination of total sulphur content on oven dried samples. Results from samples taken from the columns were compared with the results from control samples. The results of SO4 determinations are shown in Table 4. Results generally showed an increase near the surface of SO4 concentration after 3 months. However, there was considerable variation in the measured values of SO4 both between mixes and over time. These variations may have been the result of inherent variations in the material. It was difcult to determine denite accumulation of sulphate at the various depths, but the 25-mm values for mixes 2A and 3A seemed to indicate some accumulation.

4.2.3. SEM analysis Samples of cement bentonite were prepared for analysis using the scanning electron microscope SEM.. The SEM used a cryo stage and therefore it was not necessary to dry the sample, which may have caused collapse of the microstructure. The SEM analysis was intended mainly to view the mineral ettringite AFt. as a diagnostic of sulphate attack. Although AFt is present in hydrated cement

Fig. 5. Conned samples, mix 2A, after 12 months.

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AFt was found in quantities of none to easily seen in control samples, therefore an abundance of AFt was considered to be associated with sulphate attack from the contaminant solution. A summary of the SEM analysis is shown in Table 5 and examples are reproduced in Figs. 7 10. In most of the samples AFt was abundant near to the contact surface 10 mm depth. but at greater depth it was at background levels i.e. easily seen or less.. These results partly corroborate the results of chemical tests for total sulphur that indicated a higher concentration of sulphur near to the contact surface and lower concentrations within the material.
Fig. 6. Discolouration typical after conned tests, mix 4A.

5. Discussion materials, its quantity is normally restricted due to the low volume of sulphate in the cement. However, sulphate introduced from external sources can react with calcium-alumino-hydrates in the paste and result in high quantities of AFt being formed.
Table 4 Chemical analysis for SO4 in cement bentonite samples a Depthb mm. 10 25 50 100 Mix 1A 3 months 11.85 12.56 12.78 10.43 Mix 3A 3 months 10 25 50 100
a b

The durability and chemical compatibility of the cement bentonite materials used as cut-off walls are important factors in determining their potential service life and how long they will function properly in the

Mix 2A 6 months 7.1 7.24 6.35 1.79 12 months 7.02 7.23 6.6 4.84 3 months 6.78 1.98 1.84 1.88 Mix 4A 6 months 9.28 8.33 7.76 2.28 12 months 9.2 8.1 7.6 2.4 3 months 10.17 10.38 10.19 8 6 months 8.11 8.25 8.51 7.84 12 months 7 7 6.4 5.5 6 months 6.52 3.47 1.78 1.79 12 months 6.9 4.8 1.8 1.8

7.31 3.45 2.21 2.15

Values are % by weight of dry material. 100-mm columns.

Table 5 Three-month SEM analysis to monitor hydration: a summary of mix constituents present X. Feature Talc CSH Fibres AftrAFm Hexagonal AftrAFm Clinkerrslag grains pfa CaOH Ca Al H Mix 1A X X Mix 2A X Mix 3A X Mix 4A X

X X

SEM analysis for ettringite in chemically attacked samples X. Depth mm. Mix 1A 10 50 X X

Mix 2A X X

Mix 3A X

Mix 4A X X

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Fig. 7. Mix 3 at 10 mm, angular crystal of Ca Al H.

Fig. 9. Mix 1 at 50-mm depth, ettringite and CSH bres.

ground. There have been no known failures of cement bentonite barriers used in the UK, but the simple immersion test has indicated that the material can be degraded by certain contaminants or combinations of contaminants. The immersion tests used were particularly aggressive and allowed the material to expand, contract or crack freely and as such it was not representative of the in-ground situation where the material is conned. There are well-documented theories that under conned conditions the material will not crack or dissolve but will soften without increasing the permeability w15x. Whether this self-healing will occur for a wide range of cement bentonites of various cement types and mix proportions is uncertain. Some work has indicated that cracks can form in plastic concrete cut-off walls with cement bentonite as the slurry phase. and so affect contaminant transport across the barrier w28x. Whether these cracks were the result of chemical attack or other processes was not explained in the publication. The overall performance of the mixes described in this paper, immersed in solution, was moderate to very

poor at high sulphate concentrations. Magnesium sulphate was no more damaging than sodium sulphate to the cement bentonite mixes, at sulphate concentrations of 1000 mgrl. Acid H 2 SO4 . was also aggressive towards the mixes on its own and in combination with other contaminants sulphate. it was able to destroy most of the mixes in less than 1 month. Sulphate attack was expansive and led either immediately or eventually to disintegration of samples dependent on concentration. The mode of attack for acid solutions was typied by the leaching out of the hydration products which were soluble at the low pH of the solution. This leaves the samples with a lighter coloured appearance as opposed to their naturally darker colour. After sufcient material had leached out the sample disintegrated. The sulphate ions in the sulphuric acid were, however, able to produce expansion in some samples. In combined solutions of sulphate and acid the expansive reaction dominated, but the acid conditions accelerated deterioration. The best performance of these mixes was in phenol solution, a weak organic acid. The samples showed

Fig. 8. Mix 4 at 10 mm, ettringite bres.

Fig. 10. Mix 2 at 50-mm depth, ettringite and hydrating CSH.

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S.L. Gar in, C.S. Hayles r Construction and Building Materials 13 (1999) 329 341

negligible signs of attack, only some discolouration and softening of the surface was observed. Phenol, as a weak acid, will be reacting in a similar mode to that of the strong sulphuric acid, and a certain amount of the hydration products would have been removed by dissolution which gave softening of the surface. The degree of attack was, however, much less than that of sulphuric acid attack and the mixes lost an average of 7% by weight during the experimentation period. The immersion test gives valuable information on the inherent chemical resistance of a particular mix to a single contaminant or combination of contaminants. It would appear to be an adequate rst stage in assessing the suitability of a cement bentonite mix for a particular site. The chemical compatibility of the cement bentonite should be checked with site solutions including groundwaters, leachates, articial groundwaters and single priority contaminants identied from site investigation reports. A proposed cement bentonite mix may need to be rejected if there is a sufciently adverse effect on the material in the immersion test. This test would, therefore, be a screening test prior to further testing for physical parameters, leachate permeability and diffusion tests. Alternatively, if sufcient data on mix performance can be documented, then with a knowledge of site conditions, suitable mixes could be selected. However, this would require that further compliance testing be carried out in order to assure performance. In conned tests, which were intended to mirror ground conditions, attack was almost entirely eliminated for the mixes under the same strong sulphate solution. The main criteria for the tests was that there was contact between the contaminant sulphate. and the material at a surface. The lack of a signicant hydraulic head to force solution into the material meant that contaminant penetration relied mainly on chemical diffusion. There was generally an increase of SO4 concentration near to the surface of the cement bentonite, but the concentration at greater depth did not show such an increase. In agreement with this observation there was an accumulation of ettringite crystals near to the contact surface of the samples. In the future, tests will be run with a greater hydraulic head to increase contaminant penetration., and for longer, to assess deterioration patterns over greater periods of time.

particularly to contain contaminated sites. This increasing use has initiated the research on chemical compatibility, specication and long-term performance. The following points are drawn from work carried out to date.

A simple immersion test can be used to assess the chemical compatibility of cement bentonite with contaminants. Such a test is potentially of use in determining the suitability of a particular mix for a particular contaminated site. The lack of published data on mix performance means that some form of compatibility compliance tests should be used. An immersion test could be used for this purpose. It has been shown that cement bentonite can be degraded by some contaminants or mixtures of contaminants. The degree of attack was dependent on the mix proportions, type of cement used and nature and concentration of contaminants. The mode of attack was different for each contaminant. Acid solutions discoloured and softened the cement bentonite by the leaching out of hydration products, whilst the sulphate solutions produced expansion. Immersion tests showed that mixes with higher contents of PC or PCrpfa had better overall performance in all the solutions. Results suggest that a high PC content e.g. ) 150 kg. may be needed for good chemical compatibility. In conned tests, attack was almost eliminated for the mixes under the same strong sulphate solution. There was a higher concentration of total sulphur near to the contact surface; SO4 concentrations varied considerably between and within samples and this may have been due to inherent variations in the material.

Acknowledgements The authors would like to thank the Department of the Environment, Transport and the Regions of the UK for nancial support for this research. The work has been directed by an industry steering group who are also thanked. References
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6. Conclusions Cement bentonite containment barriers appear to offer a cost-effective solution to the problems of contaminated land. There have been no reports of failures of such barriers and as such their use has increased

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