Heavy Metals
Heavy Metals
Heavy Metals
12
Angelica NAKA1, Zhenze LI2, Toru INUI3, Takeshi KATSUMI4, and Hiroki MOGAMI5
The capacity of geosynthetic clay liners (GCLs) to attenuate metals and metalloids such as Al, Fe, Cu, Zn, As, and Pb
was evaluated in this study. For this purpose, free swell, sorption, and hydraulic conductivity tests on a needle-
punched geosynthetic clay liner against a pH 3 artificial acid rock drainage (ARD) were conducted. Free swelling
tests showed that at high metal concentration, the swell index decreased dramatically. Sorption test results showed
that Na-bentonite had high capacity to sorb metals and metalloids. Hydraulic conductivity tests showed that k was 10
times lower when GCL was prehydrated with water, before permeating with ARD. Effluents were also evaluated in
each case and results showed that the GCL tested has strong attenuation capacity toward metals and metalloids
present in ARD, although desorption was observed in some cases.
KEYWORDSAcid rock drainage, Geosynthetic clay liners, Hydraulic conductivity, Sorption, Swell
index
1
JGS Member, Graduate Student, Graduate School of Global Environmental Studies, Kyoto University, Japan
2
JGS Member, JSPS Postdoctoral Fellow, Graduate School of Global Environmental Studies, Kyoto University, Japan
3
JGS Member, Associate Professor, Graduate School of Global Environmental Studies, Kyoto University, Japan
4
IGS Member, Professor, Graduate School of Global Environmental Studies, Kyoto University, Japan
5
Graduate Student, Graduate School of Global Environmental Studies, Kyoto University, Japan
1
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stable under strongly reducing conditions, exposing them index of bentonite may indicate a low hydraulic
to oxidizing conditions will destabilize these rocks and conductivity. However, the presence of metals, especially
make them oxidize through a variety of mechanisms 4). multivalent cations or high concentration of monovalent
To mitigate the contamination by ARD, many cations, limits the expansion of the crystal interlayer and
remediation technologies have been proposed. Three of thus, the swell index is lower and the hydraulic
the traditional available cleanup technologies are: conductivity may increase13) 14) 15). This phenomenon is
excavation, or removal of polluted soil and proper also discussed in this research.
disposal; stabilization of toxic metals in soil, by adding
chemical agents or forcing an anaerobic environment; and
phytoremediation, or use of plants to extract heavy metals 2. MATERIALS AND METHODS
from soil or prevent the spread of contamination5). Other
new technologies propose electokinetic methods; soil Experiments were conducted using a needle-punched
flushing and washing; and the use of industrial by geosynthetic clay liner (Bentofix NSP 4900), which
products like fly ashes and slags, taking advantage of contains powered sodium bentonite sandwiched between
their high adsorption capacity toward metals2). woven and non woven geotextiles (4670 g bentonite/m2).
Since most ARD treatment technologies are usually This GCL had water content of approximately 10.0%, a
found to be inadequate, difficult, time consuming, specific gravity of 2.85, and a smectite content of 80%.
environmentally destructive, or expensive, ARD is left An artificial ARD solution was prepared in the
untreated most of the time6). Evidence that some toxic laboratory considering the composition of an acidic lake,
substances like arsenic may become mobile under caused by the discharge of acid rock drainage from a Pb-
reducing conditions7), or leaching risk because of Zn-(Cu) deposit located in Cerro de Pasco, Peru16). The
alterations in environmental conditions (e.g. changes in elemental composition of this ARD is specified in Table
pH, acid rain)2), reinforces the need for effective barriers. 1, and defined as target concentration.
Previous studies suggest that, due to its low hydraulic The artificial ARD solution was prepared by mixing
conductivity, large specific surface area and high FeSO47H2O, Al2(SO4)316H2O, CuSO45H2O,
attenuation capacity, Na-bentonite present in geosynthetic ZnSO47H2O, Na2HAsO47H2O, PbCl2, K2SO4, NaCl,
clay liners (GCLs) can be used to attenuate toxic Na2SO4, CaSO4, and MgSO4, all of them of GR grade
substances present in ARD8) 9). A recent proposal of a (Guaranteed Reagent). The pH was adjusted to 3, using
mixture consisting of limestone (40 to 75 weight percent), H2SO4. After mixing all the chemicals in the proportion
clay (10 to 35 weight percent) and magnesium oxide or specified in Table 1 (target concentration), precipitation
magnesium hydroxide (10 to 30 weight percent) that can was observed and therefore, it was necessary to filter the
efficiently control ARD, support the important role of mixture before conducting experiments. The
clay in the attenuation of heavy metals present in ARD10). concentration of each metal in solution was measured by
Metals can be immobilized in GCLs through many ICP and reported as real concentration.
adsorption mechanisms: cation exchange, surface
complexation, surface-induced precipitation, surface co- Table 1. Concentration of elements present in artificial
precipitation, colloid formation at surface, and diffusion ARD solution
into particle micropores11). Due to its large cation Target Real
exchange capacity (between 80 and 150 meq/100g), high Element concentration concentration
surface area (around 800 m2/g) and ability for interlayer (mg/L) (mg/L)
swelling9) 12), Na-montmorillonite, the principal mineral K 31.8 35.6
Na 413.9 308.4
component of Na-bentonite used in many GCLs, has a
Ca 397.0 419.7
great affinity for cations. Mg 214.0 242.2
The aim of this study was to investigate the capacity Al 259.2 273.8
of Na-bentonite to remove metal ions present in an ARD Fe 4330.2 4821.0
solution. For this purpose, hydraulic conductivity tests on Cu 86.9 88.4
prehydrated and non-prehydrated GCLs, free swelling Zn 493.1 548.6
tests and batch sorption tests on bentonite at different As 49.1 6.5
Pb 2.9 1.3
ARD concentration and bentonite amount were
systematically investigated. Free swelling tests are easy
Free swelling tests using bentonite obtained from the
to run and provide important information about the
GCL were performed according to ASTM D 5890
performance of GCLs as barrier materials. A high swell
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Standard Test Method for Swell Index of Clay Mineral using a cathetometer, and analysis of the effluent was
Component of Geosynthetic Clay Liners. Bentonite was conducted every 40 days in some cases and every week
grinded to 100% passing a 100 mesh US. Standard Sieve (one to three times per week) in others, according to the
and a minimum of 65% passing a 200 mesh US. Standard flow rate. Effluents analysis includes electrical
Sieve and then, dried for 16 hours in a drying oven at conductivity (EC), pH and volume of effluent
1055 C. After bentonite was dried to constant mass, it measurements. Metal concentration of effluents was
was allowed to cool to room temperature in a desiccator. analyzed by ICP.
Two grams of dry powdered bentonite was dusted into a
100 mL graduated cylinder filled with 90 mL of permeant
solution. After that, it was filled up to 100 mL with the
same permeant solution. The cylinder was covered and
allowed to stand undisturbed for 24 hours. After this
period, the volume level (in milliliters) was recorded.
Swell index of different dilutions of artificial ARD
solution, as well as water pH 3 (control) were evaluated.
Batch sorption tests were conducted using artificial
ARD, in order to study the heavy metal attenuation
capacity of bentonite toward multi-metal solutions.
Before conducting the tests, bentonite contained in the
GCL was grinded and dried, following the same Figure 1. Schematic view of a flexible-wall permeameter
procedure described for the swelling test. Different
amounts of bentonite (from 0.1 to 2 g) were tested using 30 kPa
25 mL of ARD solution. Also, different dilutions of ARD
solutions (from 2 to 100% ARD solution) were tested
using 0.5 g bentonite in 25 mL of solution. After 24 hours
on a shaking table at 100 rpm, the mixture was filtered
using a 0.45 m-opening filter. The concentration of each
metal before and after batch sorption tests was analyzed
by ICP (ICPS 800 Shimadzu). Permeant Solution
Hydraulic conductivity tests on GCL samples of 60 Figure 2. Method used for GCLs prehydration
mm in diameter (6 mm thickness approximately) were
conducted according to ASTM D 5084 Standard Test
Methods for Measurement of Hydraulic Conductivity of 3. RESULTS AND DISCUSSION
Saturated Porous Materials Using a Flexible Wall
Permeameter and ASTM D 7100 Standard Test (1) Effect of ARD Solution on Swell Index
Method for Hydraulic Conductivity Compatibility Results of free swelling tests using different amount
Testing of Soils with Aqueous Solutions. Permeation of ARD, as well as the final pH and EC are shown in
was performed using a falling headwaterconstant Table 2.
tailwater system, which consists of a flexible-wall Figure 3 shows the effect of different dilutions of
permeameter with a cell pressure of 30 kPa, and an ARD in swell index. The swell index of 0% ARD (or
average hydraulic gradient of 85 95, at constant room water pH 3) was 32.0 mL/2g-bentonite. This value
temperature of 25 degrees. Figure 1 illustrates the system.
Experiments were conducted using distilled water and Table 2. Effect of ARD amount on swell index
artificial ARD solution as permeants. In case of water, ARD Swell Index Final Final EC
GCLs were non-prehydrated (water was directly proportion (mL/2g) pH (mS/m)
permeated from the influent port) but, in case of ARD, 0.00 32.0 9.13 33.5
two types of prehydration were performed (using either 0.02 32.0 4.32 66.5
distilled water or artificial ARD solution). GCLs were 0.04 30.0 3.93 100.5
0.08 25.0 3.72 159.7
prehydrated for a period of 7 days, by placing them into
0.20 16.5 3.51 278.0
containments with the corresponding permeant solution,
0.40 13.0 3.35 464.0
and applying 30 kPa of pressure, according to the scheme 0.80 10.0 3.41 742.0
presented in Figure 2. Thickness of GCL was measured 1.00 8.50 3.98 1109.0
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decreased as the electrical conductivity, corresponding to For As, it was observed that the sorbed amount was
concentration of ARD in the solution, increased. As Jo et constant, even at high adsorbent concentration. In view of
al. (2001)12) indicated, when the concentration of metals the fact that bentonite does not have anion sorption
in solution increases, water moves out of the mineral capacity17) the sorbed percentage can be attributed to a
interlayer and then, reduction in swell volume occurs. In surface complexation sorption mechanism of As on
addition, since the initial and final pH of all tested ARD Fe(OH)3. The sorbed percentage of Pb was not plotted
solutions were around 3.5, the reduction on swell volume because the initial concentration was very low (1.3 mg/L)
can be only attributed to the metals present in ARD. and the dilution level made for ICP analysis (100 times
dilution) did not allow Pb detection.
35
Figure 5 shows sorbed percentage of Na, K, Ca and
Swell index (mL/2 g bentonite)
0 Na
0 200 400 600 800 1000 1200 100
K
Ca
Sorbed percentage (%)
EC (mS/m) 0 Mg
-100
Figure 3. Effect of ARD concentration on swelling of
bentonite from GCL -200
-300
(2) Sorption Test of Artificial ARD on Different Amount
of Bentonite -400
0 20 40 60 80
Figure 4 shows the sorbed percentage of each metal
Bentonite amount (g/L)
present in ARD, using different amount of bentonite
(from 4 to 20 g bentonite/L solution). Sorbed percentage Figure 5. Sorbed percentage of Na, K, Ca and Mg present
was calculated by dividing sorbed amount (initial minus in ARD solution
final concentration) by initial concentration. In case of Cu
(initial concentration, 88.4 mg/L) and Al (initial (3) Sorption Test of Artificial ARD on Bentonite at
concentration, 273.8 mg/L), 100% of these metals were Different ARD Percentages
sorbed by 80 g/L of bentonite. Around 45% of Zn (initial Figures 6 and 7 show the sorbed percentage of metals
concentration, 548.6 mg/L) and 75% of Fe (initial present in different ARD diluted solutions (from 2 to
concentration, 4821.0 mg/L) were sorbed by 80 g/L of 80% ARD), using 20 g/L of bentonite. When ARD
bentonite. proportion was around 0.1 (or 10% diluted ARD) all
metals were completely sorbed on bentonite, except As,
in which case only 0.2% were sorbed. At 0.8 ARD
Fe
100
Cu proportion (or 80% ARD), around 25% of Fe, 33% Cu,
Zn
11% Zn, 77% Al, 80% As and 16% of Pb were sorbed on
Sorbed percentage (%)
80
Al
60
As bentonite. In case of As, an abnormal behavior was
observed, because at high ARD concentration, the sorbed
40
percentage was high too. As mentioned before, this
20
phenomenon can be attributed to the sorption of As on
0 Fe(OH)3.
-20 Figure 8 shows the amount of metal sorbed per gram
0 20 40 60 80
of bentonite, using different ARD proportion. This figure
Bentonite amount (g/L)
is composed of three graphs, according to the range they
Figure 4. Sorbed percentage of metals present in ARD fitted better. These figures show that even at high ARD
solution concentration (80% ARD) and low pH (pH = 3), high
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amount of metals were retained by bentonite. However, a
a) Fe
saturation point was observed in case of Fe, Zn, Cu and 1
Al
Pb. The maximum amount of Fe sorbed was around 0.85
Amount sorbed
0.6
was around 0.02 mmol/g of bentonite, for Zn, around
0.035 mmol/ of g bentonite and for Pb, around 0.00004 0.4
mmol/g of bentonite. In case of Al, the sorbed amount at
0.2
80% ARD was around 0.3 mmol/g of bentonite and, in
case of As, 0.003 mmol/g of bentonite. 0
0 0.2 0.4 0.6 0.8
Figure 9 shows that high amount of Na, K, Ca and Mg
ARD proportion
were released from the bentonite. It supports the fact that
the mechanism involved corresponds to ion exchange.
b)
Cu
0.04
Fe Zn
100 As
Amount sorbed
80 Al
As
Pb 0.02
60
40 0.01
20
0
0 0.2 0.4 0.6 0.8
0
0 0.2 0.4 0.6 0.8 ARD proportion
ARD proportion
3
Amount sorbed
Na
500
K 2
0 Ca
Sorbed percentage (%)
Mg
-500
1
-1000
-1500 0
0 0.2 0.4 0.6 0.8
-2000
ARD proportion
-2500
ARD proportion
(b) and Pb (c) at different ARD diluted solutions
0
Mg
As the sorption performance of bentonite was greatly -0.1
Amount sorbed
5
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(4) Hydraulic Conductivity Tests Using Artificial ARD part of the As is prevented from breaking through the
Solution GCL by the Fe sorbed or precipitated into it. Fe
Changes in hydraulic conductivity values (k) versus experienced strong retention and the evidence of a
pore volumes of flow (PVF) are illustrated in Figures 10, red/orange layer of iron hydroxide in the GCL, observed
11 and 12. PVF was calculated by dividing the by Lange et al18), supports this hypothesis. Figure 14
cumulative amount of effluent collected during the test illustrates the release of high amount of Na, Mg, K, and
(m3) by the volume of voids in the specimen (m3). The Ca from GCL, which stabilize after 50 PVF.
hydraulic conductivity of GCL permeated with distilled
water (Figure 10) was constant, with an average value of 1x10 -9
after 5 PVF, and rose to 2.8 10-10 m/s after 65 PVF and
5.8 10-10 m/s after 200 PVF (3 times larger) .
1x10 -12
Effluents from distilled water permeation through 0 2 4 6 8 10 12 14
GCL showed Na, Mg, K and Ca, which are present in
Pore volumes of flow, PVF
GCL, were released. The pH was around 9.3, and the EC
was 0.62 S/m after 6 PVF and decreased to 0.34 S/m after Figure 10. Hydraulic conductivity for GCL permeated
12 PVF. with distilled water
Effluent from ARD permeation through prehydrated
GCLs showed that after 3 PVF only Na, Mg, K and Ca 1x10 -9
Hydraulic conductivity, k (m/s)
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From the results of permeation with ARD, a ARD. Eighty grams per liter of bentonite adsorbed 100%
relationship between k and pH was observed. The of Al and Cu; 45% of Zn, and 75% of Fe. Negative
increase in hydraulic conductivity matched up with the values of adsorbed percentage observed for Na, K, Ca,
fall in pH, which is a phenomenon explained by Lange et and Mg indicate that these cations are released from
al (2005)18). They stated that an increase in hydraulic bentonite and therefore, the mechanism involved likely
conductivity is probably due to pore space opening when corresponds to cation exchange.
cations were mobilized by the adsorption of H+ and/or The hydraulic conductivity for distilled water was
degradation of the bentonite from the acid. This theory is constant and around 2.5 10-11 m/s. The k value for the
corroborated by results obtained, in which release of GCL prehydrated with distilled water and permeated with
metals or exchange of metals with H+ was observed. ARD was 1.4 10-11 m/s after 5 PVF, and increased
gradually to values between 2.0 10-11 and 3.0 10-11
m/s. The hydraulic conductivity of the GCL prehydrated
Fe
300
Cu with artificial ARD solution also increased gradually and,
Zn
after 65 PVF, it rose to 2.8 10-10 m/s. Prehydration of
Released percentage, %
250
Al
200
As GCL with ARD solution, which is equivalent to a non-
Pb
prehydration case, lead to a 10 times increase of the k
150
value, compared with the water prehydrated GCL case. A
100
relationship between swell index and hydraulic
50 conductivity was observed. In cases of ARD permeation
0 (low swell index), the hydraulic conductivity was higher
0 50 100 150 200 250
than in case of water permeation (high swell index).
Pore volumes of flow, PVF
Moreover, prehydration seemed to prevent from rapid
Figure 13. Released percentage of Fe, Cu, Zn, Al, As and increasing of k.
Pb of ARD permeated and prehydrated GCL The effluent analysis showed that, after water
permeation, the release of Na, Mg, K, and Ca turned the
solution alkaline. After 12 PVF of permeation with ARD
Na
1000
Mg through the water prehydrated GCL, small amounts of Fe,
K
Released percentage, %
800
Cu, Zn, Al, As, Pb, and high amount of Na, Mg, K, and
Ca
Ca were released. Results of ARD permeation through
600
the ARD prehydrated GCL showed high metal
400 attenuation capacity of GCL after determined PVF for
each metal.
200
Even though prehydration can improve the hydraulic
0 conductivity of the GCL by making it lower, the
0 50 100 150 200 250
treatment method for ARD should include other
Pore volumes of flow, PVF
considerations, as it was observed that the hydraulic
Figure 14. Released percentage of Na, Mg, Ca, and K of conductivity tends to increase after some time of
ARD permeated and prehydrated GCL permeation with ARD and metal desorption also occurred.
4. CONCLUSIONS ACKNOWLEDGEMENTS
The Nikkei Scholarship granted by The Nippon
The swell index is proportional to EC or the amount Foundation (Nippon Zaidan) has been provided to the
of metals in solution. The swell index of distilled water first authors postgraduate study. The authors express
adjusted to pH 3 using H2SO4 was 32 mL/2 g bentonite, deep gratitude to Dr. Giancarlo Flores (Kyoto University),
which decreased as the proportion of ARD increased. Dr. Takehiro Ohta (Railway Technical Research Institute),
Thus, at 2% ARD the swell volume was 32 mL/2 g and Mr. Takuya Urakoshi (ditto) for their helpful
bentonite, at 20% ARD the swell index was 16.5 mL/2 g discussions and constructive comments and suggestions.
bentonite, while at 100% ARD the swell volume was 8.5
mL/2 g bentonite.
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Angelica NAKAZhenze LI
GCLsAlFeCuZnAsPb
GCLs
Na
GCLs
10
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