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The Retention Characteristics of Heavy Metals in Natural Soils using Soil

Column Experiment

Article · January 2008

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 th
The 12 International Conference of
International Association for Computer Methods and Advances in Geomechanics (IACMAG)
1-6 October, 2008
Goa, India

The Retention Characteristics of Heavy Metals in Natural Soils

using Soil Column Experiment
Wan Zuhairi W.Y., Abdul Rahim Samsudin, & Nurita Ridwan
Geology Programme, School of Environmental and Natural Resource Studies, Faculty of Science and
Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor.

Key Words : heavy metals, soil column, natural soil, breakthrough curve, retention

ABSTRACT: Column experiment is a very useful apparatus that can be used to study the migration and
attenuation of heavy metals (HMs) through a compacted soil column. In this recent study, column experiment
was conducted on some natural soils from Selangor area in Malaysia using different types of heavy metals,
namely Pb, Cu, Ni and Zn. Prior to testing, all soils were thoroughly characterized for their physical, chemical
and mineralogical properties. Three soil samples, namely Sungai Besar marine clay (SBMC), and weathered
metasediments from Batang Berjuntai (HMS) and river alluvium soil from Ampar Tenang (ARA) were used in this
study. All soil columns were permeated using laboratory made solution with concentrations of heavy metals
ranging from 516-567 mg/L, pH was 1.5 and conductivity 5.93 mS/cm. The experimental test results were
analysed in terms of their breakthrough curves, and the retention-migration profiles from top to bottom of the soil
column. The breakthrough curves show that the SBMC sample has better adsorption capacity on heavy metals
compared to other soils; resulting less migration of heavy metals through the soil column. Less retention means
high concentration of heavy metals is detected in the pore fluid. the test result also reflect the influence of soil
origin in adsorption of heavy metals, where soil characteristics and surface properties contribute very significantly
to the adsorption of heavy metals by soils.

1 Introduction
Soils have been widely used as natural and/or compacted clay liner underneath the landfill sites to prevent the
seeping of the leachate into the environment. The use of clay soils as impermeable or attenuating barriers is
becoming more popular as the “material of choice” in landfill liner systems. Many researchers (Griffin et al., 1976;
Yanful et al. 1988; Yong et al. 1992, 1993, etc.) have discussed the different aspects and potential use of soil
material not only for liners, but also as substrate material under landfills. The behaviour of heavy metals in soils
has also been extensively studied and published during the past 20 years (Antoniadis and McKinley, 2000;
Anderson and Christensen, 1988; Wan Zuhairi, 2003a; 2003b, and etc). Soils have the capability to physically
and chemically retard the movement of leachate. Soil can be compacted to achieve very low hydraulic
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conductivity of less than 1x10 m/sec and acts as a final protection for groundwater against a leachate.
Malaysian Department of Environment requires the hydraulic conductivity value of 1x10-9m/sec. Soil is a product
of accumulation of different active components such as clay minerals, organic matters, carbonate fractions and
oxy/hydroxides amorphous materials. These components are chemically reactive and react with various types of
contaminants resulting attenuation of contaminants in the soil system.

In the present study, compacted soil in plexiglass column (i.e. soil column experiment) was tested against high
concentration of heavy metals (HMs). Soil column is a very useful physical tool to study the migration of
contaminants through a compacted soil. It is used to model the migration of HMs in soil and very useful for
numerical and/or experimental studies. This paper explains the soil column experimental results undertaken on
selected soils from Malaysia. The soils have been used in Malaysian landfills.

2 Materials and Methods

Fifteen samples from three different soils, namely Sungai Besar marine clay (SBMC1-5), and weathered
metasediments from Batang Berjuntai (HMS1-5) and river alluvium soil from Ampar Tenang (ARA1-5) were
collected from Selangor area in Peninsular of Malaysia (see Figure 1). All samples were subjected to physical
and chemical tests. Physical tests comprised of particle size distribution, Atterberg Limits, compaction, specific
gravity and permeability, using standard methods of BS1377 (1990). Chemical tests consisted of soil water pH
(1:10 ratio), organic matter, carbonate contents, amorphous oxides/hydroxides, specific surface area (SSA) and
cation exchange capacity (CEC). All chemical tests were conducted using a method suggested by Mc Gill

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University Geotechnical Research Centre Laboratory Manual (1985).

Figure 1. The sampling locations of three different soil in Selangor, Malaysia.

Soil column experiments were conducted on these three samples based on previous column model as suggested
by Yong (2001) and Wan Zuhairi (2000). This new physical model were redesigned and built to reduce leakage
especially along the contact after different components of column apparatus were put together. This rather new
soil column consisted of plexiglass cylinder with a diameter of 100mm and length of 104mm. Column apparatus
is comprised of two parts; first top part is a leachate reservoir and the bottom part is a place for compacted soil
(Figure 2). Glass microfiber filters (Whatmann) were placed on the porous disc at the top and bottom ends of the
columns to prevent influx and outflux of particles. Each sample was tested in a series of duplicate column with a
label of 3PV and 5PV, where PV represents the pore volume of the soil. A pore volume (PV) is defined as the
volume necessary to displace the volume of interstitial liquid in the pore spaces within the soil column. Soils at
their optimum moisture content (Wopt) were compacted in three separate layers in the plexiglass cylinder
according to a standard Proctor compaction test using 25kg weight hammer. All components were attached
together and screwed tightly to prevent any leakage. There were two stages of leaching for column test; (i)
saturation stage using deionised distilled water; and (ii) leaching stage using a test solution. The leaching
experiments were conducted under constant air pressure of 10psi (i.e. equivalent to hydraulic gradient, i ~ 68) to
reduce the time factor for test solution transport through the soil columns. The chemical composition of spiked
test solution is given by Table 1 below. The use of spiking is to increase the contaminant concentrations and is
very useful to study more extreme conditions of contaminant attack, i.e. a procedure which maximise the
contaminant-soil interaction effects. The pH of the leachate was also reduced to 1.5 to increase the mobility of
the heavy metals and to prevent any accumulation of the heavy metals inside the reservoir (i.e. heavy metals are
precipitated when pH>5.5). After every 0.5PV of leaching, the effluents were collected and analysed using
ICPMS. All effluents were filtered using Whatmann cellulose nitrate filter papers (<0.2 μm pore with 47-mm
diameter) prior to analyzing to prevent blockage of ICPMS tubes.

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 Figure 2. The schematic diagram of column experiment on three different soils.

Table 1. The composition of test solution.

Parameter Value
Pb 538.6
Cu 556.8
Zn 516.8
Ni 567.9
pH 1.5
Conductivity 5.93 mS/cm
All concentration in mg/L except for pH and conductivity

3 Results and discussions

3.1 Physico-chemical properties

Yong et al. (1993) stated that the relatively low hydraulic conductivity and high adsorption capacity of clay soils
make them prime candidates for constructed or engineered clay barrier. Table 2 and 3 below show the physical
and chemical properties of all soils used in this study. The specific gravity values for all soils were found to be
very similar and did not show much variation between soils, being in the range between 2.2 and 2.7. Soil HMS
and ARA contained high percentage of sand with the values ranged from 11% to 45%. Note that soil SBMC
contained high composition of fine fractions (i.e. silt plus clay). The average permeability value for SBMC was
found to be low compared to HMS and ARA, and this is due to the high composition of fine fractions in SBMC soil.
Soils SBMC and HMS can therefore be classified as clay with high plasticity (CH), while soil ARA was classified
as silt with low plasticity (ML). This classification was made from the soil Atterberg limits values (i.e. LL, PL, and
PI).

Table 2: Physical properties of three soils from Selangor, Malaysia

Soils Gs S (%) M (%) C (%) LL PL PI (%) Wopt γdmax K (x10-9) Clas
(%) (%) m/sec s
SBMC 2.2- 2-8 46-60 33-52 50- 18-28 27-45 29.32 1.4-1.4 7.9 CH
2.3 68
HMS 2.4- 11-15 45-56 20-30 39- 21-27 14-35 21-30 1.3-1.5 23.8 CH
2.7 57
ARA 2.2- 2-45 42-71 10-27 39- 24-32 11-25 10-22 1.5-1.6 513 ML
2.4 50
Gs= Specific gravity; LL=liquid limit; PI=plasticity index; ; S=Sand; M=Silts; C=Clay; γdmax=Maximum dry density;
Wopt=Optimum moisture content; K = Hydraulic conductivity; CH = clay with high plasticity; CL = clay with low
plasticity; ML = silt with los plasticity

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The chemical parameters for all soils are presented in Table 3. The pH values of all soils were found to be very
different. Soil ARA pH values were acidic, ranged between 4.2 and 4.5. pH values of SBMC soils were alkaline,
ranged from 7.2 to 7.5. The pH of HMS was found to be intermediate (the values between 6.2 and 7.4). Based
on Table 3, SBMC soils contain high organic, carbonate, CEC and SSA compared to soils HMS and ARA. The
difference of above soil chemical parameters observed in Table 3 was due to the presence of an active clay
mineral called montmorillonite in soils SBMC. Montmorillonite, which is an active clay mineral that increases the
CEC and SSA values in SBMC soils. However in other soils, montmorillonite is absent and contain mainly of
kaolinite and illite, resulting small values of SSA and CEC. According to William (1997), montmorillonite has
higher SSA (600-800 m2/g) and CEC (80-100meq/100g) values compare with kaolinite and illite (SSA 5-20 m2/g
and CEC 3-15 meq/100g).

Table 3: Chemical properties of three soils from Selangor, Malaysia

Soils pH Organic (%) Carbonate (%) CEC (meq/100g) SSA (m2/g) Mineralogy
SBMC 7.2-7.5 5-14 9-13 25-75 90-138 M, I
HMS 6.2-7.4 3-13 8-13 1-6 20-36 K, I
ARA 4.2-4.5 3-11 4-15 1-9 12-16 I

SSA = specific surface area, CEC = cation exchange capacity; K = Kaolinite; I = Illite; M = Montmorillonite; SBMC
= Marine clay from Sg Besar; ARA = River alluvium soils from Ampar Tenang ; and weathered metasediments of
Batang Berjuntai (HMS), Air Hitam (PMS) and Sg Kembong (KMS).

3.2 Breakthrough Curves and retention assessments

The breakthrough curves (BTCs) are plotted between relative concentration (Ce/Co) against the pore volumes.
Relative concentration (Ce/Co) is a ratio between concentration of HMs in the effluents and concentration of HMs
in the influent. The relative concentration equals 1.0 represents the total breakthrough of HMs through the
compacted soil column. In this paper only the results from 5 PV columns will be discussed.

Figure 3 shows the BTCs of Pb, Cu, Ni and Zn for SBMC soil as observed in soil column PV5. It can be seen
that Ce/Co values were increased with the increasing numbers of pore volumes. The plots also showed that Ni
and Zn were the most mobile heavy metals, with the Ce/Co after 5PV was 0.6. Low Ce/Co values (i.e. BTCs < 1.0)
showed that sorption of heavy metals was high. The BTCs indicated that different heavy metals have different
affinity (or selectivity) for sorption, where the affinity of HMs sorption can be ranked as Pb>Cu>Ni ≈ Zn. The
sorption of heavy metals in soil column in Figure 3 also corresponded very well with the buffering capacity of the
soil as indicated by the pH line. The pH line were almost constant from the start to end, with the values ranged
from 6.5-8. Note that the pH of the inffluent (i.e the test solution) was about 1.4. The pH profile showed that
SBMC soil has a very good buffering capacity, i.e soil has good capacity to resist any changes from an acidic test
solution to maintain its pH from start to the end of the test.

0.7 9
Pb Cu Ni Zn pH
8
0.6
Relative concentration (Ce/Co)

7
0.5
6
0.4 5

0.3 4

3
0.2
2
0.1
1

0 0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Number of pore volumes (PV)

Figure 3. The breaktrough curves for SBMC (5PV)

Figure 4 shows the BTCs of HMS soil after 5PV of column leaching tests. The Ce/Co values were below the total
breakthrough value of 1.0, although Ni showed higher moblility (less sorption) in the soil column with the values

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of 0.8. Interesting to note that after 3 pore volumes of leaching, Ni breakthrough was slowly decreased (25%
decreasing from Ce/Co = 0.8 to Ce/Co=0.6). It is also interesting to note that the mobility of Pb in the column was
quite high as compared to Pb in SBMC soil column. However, the Ce/Co values were small, i.e. less than 0.3.
The affinity for sorption in this soil column can be ranked as Zn ≈ Cu>Pb>Ni. This new affinity order for sorption
in HMS is so much different as shown earlier in SBMC soil (Figure 3), probably due to the different physical and
chemical properties of these two soils. The pH line also showed a drastic plunging in HMS soil column with an
early pH values was 7.0 to a final pH values of 5.0. Based on the pH line behaviour, one may conclude that HMS
soils posses low buffering capacity, and this was an explanation to the behaviour pattern for Ni in the column (i.e.
poor buffering will increase the mobility of heavy metals and decreasing the ability for sorption in soils).
0.9 8

0.8 Pb Cu Ni Zn pH
7
Relative concentration, Ce/Co
0.7
6
0.6
5
0.5

pH
4
0.4
3
0.3
2
0.2

0.1 1

0 0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Number of pore volumes, PV
Figure 4. The breaktrough curves for HMS (5PV)

Figure 5 shows the BTCs for ARA soils. The Ce/Co values for PV5 soil column was below 0.14. Ni showed
highest mobility in ARA column, similar to that observed earlier in soil HMS. Zn and Cu showed the least mobile
of heavy metals. The affinity for sorption in this column can be ranked as Zn ≈ Cu>Pb>Ni; which is similar as
previously observed in HMS soil columns. The pH values were quite constant (pH 4.0) in the 5PV soil column.
The pH values shown in the column were in an acidic region and may well indicate the poor buffering capacity of
this soil.

Figure 6 shows the pH lines of three compacted soils after 5PV of leaching. It was observed that after 5PV of
leaching using pH 1.5 test solutions, soil SBMC showed very high resistance to an acidic test solution, where the
pH values throughout the test were in an alkaline region with the values of pH 8 - 7. This undoubtedly shows that
soil SBMC has a very good buffering capacity and be able to buffer an acidic solution that act upon it. Since the
pH values for the effluents showed a range of 6 to 8, one may conclude that all the heavy metals were
precipitated in the soil columns -- as confirmed before by the study of Yong and Phandungchewit (1993).

0.14 4.5
Pb Cu Ni Zn pH
4
0.12
Relative concentration, Ce/Co

3.5
0.1
3
0.08 2.5
pH

0.06 2

1.5
0.04
1
0.02
0.5

0 0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Number of pore volumes, PV
Figure 5. The breaktrough curves for ARA (5PV)

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Soils HMS and ARA were not very good to buffer an acidic test solution. The pH values for HMS were in an
alkaline region (pH 7.5) at the start of the test (PV1) but the pH decreased to an acidic region with further addition
of test solution (final pH was 6). The worst soil to buffer an acidic test solution was shown by soil ARA, where the
pH values were in an acidic region from start to the end of testing (final pH 4.0). This demonstrated that soil ARA
could not resist an acidic attack that was applied to it by an acidic test solution. In terms of soil buffering capacity
of these soils, one may conclude that soil SBMC has the highest buffering capacity followed by soil HMS and
ARA. The buffering capacity of these three soils can be ranked as SBMC>HMS>ARA.

The buffering capacity parameter plays very important role in the retention of heavy metals. Soil with high
buffering capacity retains most of the heavy metals as compared to soil with the lowest buffering capacity. In the
present study, soil SBMC had a capacity to retain all heavy metals in the test solution as given by Figure 7 (only
Pb is shown here). Soils ARA and HMS had a lower retention capacity which were given by low values of Ce/Co.
However, the retention behavior of HMS and ARA in Figure 7 was very confusing, as it was contradicted with the
soils’ buffering capacity (Figure 6) and physical chemical properties (Table 2 and 3). Based on the soils buffering
capacity and soils physical chemical properties, one may conclude that soil HMS is better than soil ARA in terms
of its capability to retain the heavy metals. However, the breakthrough curves in Figure 7 showed otherwise,
whereby the retention of ARA was better than HMS. The reason for this behavior was probably due to the
appearance of channel during testing (microfracture) in HMS soil column, resulting more heavy metals seeped
through the compacted soil column. Further investigation is required to clarify this phenomenon.

6
pH of effluents

1
SBMC_Pb_5PV HMS_Pb_5PV ARA_Pb_5PV

0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Number of pore volumes (PV)

Figure 6. The pH lines of three compacted soil columns SBMC, HMS and ARA.

0.25
SBMC ARA HMS
Relative Concentration (Ce/Co)

0.2

0.15

0.1

0.05

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Number of pore volumes (PV)

Figure 7. The comparison of Pb retention in three different soil columns SBMC, HMS and ARA.

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 4 Conclusions
The study has revealed that soils have different capacity to retain heavy metals (HMs) and very much depending
on their physical and chemical properties. The affinity or selectivity of HMs for sorption (or retention) also varies
in different types of soils, as been proven by the study. Based on the physical-chemical properties, soil SBMC is
a good candidate to be selected to function as engineered clay liner. Soils HMS and ARA are also useful, but
certain additives have to be added to improve the soil (eg. using bentonite).

The study also revealed that column test is a good experimental tool to assess the retention capability of the soils
on HMs, as shown by this study using a breakthrough curves. Soil SBMC has a capability to retain most of the
HMs, and also has good buffering capacity to maintain its pH against acidic solution (pH 1.4), therefore
increasing the chances of retaining most of HMs via natural attenuation (i.e. precipitation). The study also
concludes that soil SBMC has a very good potential to function as liner material compared to two other soils,
namely ARA and HMS.

5 Acknowledgements
The results presented in this paper are part of the project funded by E-Science Fund 04-01-02-SF0153 from The
Malaysian Ministry of Science, Technology and Innovation (MOSTI).

6 References
Anderson, P.R. and Christensen, T.H. (1988). Distribution coefficients of Cd, Co, Ni and Zn in soils. Journal of Soil Science,
Vol. 39, pp 15-22

Antoniadis, V. & McKinley, J.D. 2000. Leaching tests in a laboratory centrifuge on zinc migration in London Clay. International
Symposium on Physical Modeling and Testing in Environmental Geotechnics, France. 50-58

British Standard Institution, BS1377. 1990. Method of Test for Soils for Civil Engineering Purposes. Geotechnical Research
Centre Laboratory Manual 1985. Laboratory Manual. Mc Gill University, Montreal Canada. (unpubl.)

Griffin, R.A., Shimp, J.D., Steele, J.D. Ruch, R.R., White, W.A., and Hughes, G.M. (1976). Attenuation of Pollutants in
Municipal Landfill leachate by Passage through Clay. Environmental. Science and Technology. Vol. 10 pp. 1262-1268.

Wan Zuhairi W.Y. 2000. An investigation of natural attenuation characteristic of natural clay soils from South Wales and
their potential use as engineered clay liner. Thesis Doctor of philosophy (Ph.D.). Cardiff University (unpublished)

Wan Zuhairi W.Y. 2003a. Sorption capacity on lead, copper and zinc by clay soils from South Wales, United Kingdom. Journal
of Environmental Geology, 45(2): 236 - 242.

Wan Zuhairi, W.Y. 2003b. Heavy Metal Sorption Capabilities of some Soil Samples from Active Landfill Sites in Selangor.
Geological Society of Malaysia, Bulletin 46, pp 295-297.

Yanful, E.K., Quigley, R.M., Nesbitt, H.W., 1988. Heavy Metal Migration at a Landfill site, Sarnia, Ontario, Canada—2: Metal
Partitioning and Geotechnical Implications. Applied Geochemistry, Vol. 3, pp. 623-629.

Yong, R.N., Mohamed, A.M.O & Warkentin, B.P. 1992. Principles of Contaminant Transport in Soils. Elsevier, New York.

Yong, R.N. & Y. Phandungchewit, 1993. PH Influence on Selectivity and Retention of Heavy Metals in Some Clay Soil. Can.
Geotech. J. 30: pp. 821-833.

Yong, R. N. 2001. Contaminated soils, pollutant fate and mitigation. CRC press, New York.

William, J.D. 1997. Groundwater chemistry: Fundamental and application to contamination. Lewis publisher.

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