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Effect of acidic mine drainage on the polymer properties of an HDPE

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Article  in  Geosynthetics International · January 2004

DOI: 10.1680/gein.11.2.60.46851

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 Geosynthetics International, 2004, 11, No. 2

Effect of acidic mine drainage on the polymer

properties of an HDPE geomembrane
S. B. Gulec1, T. B. Edil2 and C. H. Benson3
1
Senior Staff Engineer, GeoSyntec Consultants, 1100 Lake Hearn Driver, Suite 200, Atlanta,
GA 30342, USA, Telephone: +1 404 705 9500, Telefax: +1 404 705 9400, E-
mail: bgulec@geosyntec.com
2
Chairman of Geological Engineering and Professor, Department of Civil and Environmental
Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI 53706, USA,
Telephone: +1 608 262 3225, Telefax: +1 608 263 2453, E-mail: edil@engr.wisc.edu
3
Professor, Department of Civil and Environmental Engineering, University of Wisconsin-Madison,
1415 Engineering Drive, Madison, WI 53706, USA, Telephone: +1 608 262 7242,
Telefax: +1 608 263 2453, E-mail: benson@engr.wisc.edu

Received 10 September 2003, revised 8 February 2003, accepted 11 February 2004

ABSTRACT: A laboratory exposure programme was conducted to assess the effects of acidic mine
drainage (AMD) from metallic mine wastes on the bulk polymer properties of a 1.5-mm-thick HDPE
geomembrane. Coupons of the geomembrane were immersed in tanks containing a synthetic AMD
maintained at 20, 40 and 608C. Two other solutions (acidic water and deionised water at 20, 40, and
608C) were also used. Specimens were periodically removed from the tanks and tested to determine
whether changes were occurring in the melt flow index (MFI), polymer structure (as determined by
Fourier transform infrared spectroscopy, or FTIR), and oxidation induction time. Only modest
effects of AMD exposure were observed in the MFI and FTIR tests over the 22-month exposure
period. The OIT changed appreciably during exposure, and followed a first-order (exponential in
time) degradation pattern. Greater depletion rates occurred at higher temperatures and in the
chemical solutions. An Arrhenius model was used to estimate the antioxidant depletion time for
HDPE geomembranes immersed in AMD. Conservative estimates of the depletion time range from
46 years to 426 years depending on field temperature, initial OIT, and exposure condition.

KEYWORDS: Geosynthetics, Acid mine drainage, AMD, Compatibility, Durability, HDPE

geomembrane, Lifetime prediction, Mine waste, OIT, Tailings, Waste rock

REFERENCE: Gulec, S. B., Edil, T. B. & Benson, C. H. (2004). Effect of acidic mine drainage on
the polymer properties of an HDPE geomembrane. Geosynthetics International, 11, No. 2, 60–72

1. INTRODUCTION prevent leakage and to collect leachate for treatment.

Acid mine drainage (AMD), the leachate from waste
rock and tailings from mining and beneficiation of
sulfide-rich ores, poses a threat to groundwater and
surface water at mine sites worldwide. AMD is formed
when sulfide-rich mine wastes oxidise in the presence of
water, and is characterised by low pH and elevated
concentrations of metals, some of which are toxic. The
most common elements found in AMD are sulfur, iron,
copper, zinc, silver, gold, cadmium, arsenic and uranium
(Ripley et al. 1996).
Modern mining operations deal with the risks of
groundwater contamination by placing mine wastes in
engineered waste containment facilities designed using
principles employed for solid waste landfills (Almeida
et al. 2002; Brennecke and Corser 1998; Van Zyl and
Simpson 1997). These mine waste containment facilities
make extensive use of geosynthetics, such as geomem-
branes, geotextiles and geocomposite drainage layers, to
1072-6349 # 2004 Thomas Telford Ltd
Because geosynthetics play a pivotal role in the effec-
tiveness of these waste containment facilities, the long-
term compatibility of geosynthetic materials in contact
with mine waste leachates (and AMD in particular) is
important. However, little information currently exists in
the literature regarding how mine waste leachates affect
geosynthetic materials (Gulec 2003).
This paper describes part of a study conducted to
evaluate how exposure to AMD from metallic mine
wastes affects the properties of geosynthetic materials
used in mine waste containment. A geomembrane,
geotextile and drainage geocomposite were immersed in
tanks containing synthetic AMD, acidic water and
deionised (DI) water at 20, 40 or 608C. Samples were
removed from the tanks periodically and tested to
determine whether exposure to the test liquids affected
their bulk properties. Effects on the polymer properties
of the geomembrane are described in this paper. Polymer
properties were investigated because the durability of
60
Effect of acidic mine drainage on the polymer properties of an HDPE geomembrane 61

geosynthetic materials depends largely on the composi- 1985; Klemchuk 2002). Oxidative attack has been
tion of the polymers from which they are made as well as reported to have particularly severe impact on poly-
on conditions during the fabrication process (Cassidy olefins (e.g. polyethylene and polypropylene) (Horrocks
et al. 1991). Effects of exposure on the mechanical et al. 1997; Sangam and Rowe 2002).
(trapezoid tear strength, puncture strength, and wide-
strip tensile strength) and hydraulic (permittivity, 2.2. Oxidation of polyethylene
transmissivity) properties of the geosynthetics are
Oxidation of polyethylene is an auto-accelerating pro-
described by Gulec et al. (2004). In general, no
cess, meaning that the rate is slow at first, but gradually
statistically significant changes in the mechanical or
accelerates. The period before oxidation accelerates (and
hydraulic properties of the geosynthetics occurred
measurable degradation takes place) is called the
during the 22-month exposure period.
‘induction period’ (Hsuan and Koerner 1998). When
polymer degradation due to auto-oxidation chain reac-
2. BACKGROUND tions becomes severe, alteration of the physical and
mechanical properties of polymers occurs (Hsuan and
2.1. Degradation of geosynthetics Koerner 1998).
Oxidation of polyethylene is caused by an auto-
The following mechanisms can degrade geosynthetics,
oxidation chain mechanism that involves two interacting
depending on the nature of exposure and the type of
cyclical processes, shown as Circle A and Loop B in
polymer: UV light, radiation, elevated temperatures,
Figure 1. Circle A consists in the formation of
chemical disintegration, mechanical damage and oxida-
hydroperoxide (ROOH) and free radicals, and Loop B
tion (Haxo and Nelson 1984; Koerner et al. 1990).
consists in decomposition of the hydroperoxide to form
Degradation generally begins as changes in the polymer
more free radicals (Grassie and Scott 1985). The
structure and eventually is manifested as changes in
degradation reactions start with generation of a free
engineering properties (e.g. mechanical and hydraulic
radical (R
) (any species that contains one or more
properties) of geosynthetics (Hsuan and Koerner 1998).
unpaired electrons, which make the species reactive)
Common changes in the polymer include embrittlement,
from the polymer chain (RH):
reduction or gain in molecular weight, generation of free
radicals, loss of additives and plasticizers, and impair- RH ! R
þ H
ð1Þ
ment of transparency (Kulshreshtha 1992).
Identification of a single dominant degradation Catalysts, heat or UV light can initiate chain scission in
mechanism for geosynthetics used in mine waste liner the polymer, generating free radical species (Fay and
systems is not possible because, in most cases, more than King 1994). After the free radical is generated, it reacts
one of the listed degradation mechanisms is encountered. with oxygen and forms peroxy radical (ROO
) (Circle
However, some of the aforementioned degradation A):
mechanisms are unlikely for mine waste applications.
Geosynthetics are buried in liner applications, which R
þ O2 ! ROO
ð2Þ
eliminates UV degradation except during construction.
The peroxy radical (ROO
) then abstracts a hydrogen
Radiation generally is not important because radioactive
atom from the surrounding polymer chain to form
materials generally do not exist in appreciable quantities
in most metallic mine wastes (except those associated
with uranium mining). Thermal degradation (i.e. degra-
dation of a polymer at elevated temperatures without the O2

involvement of another compound) is negligible at

Start of
common environmental temperatures (Schnabel 1981) reactions
except near seams, and microbiological attack is unlikely
RH (Polymer chain) (a)
owing to the high molecular weight of polymer resins
used in geosynthetics (Koerner et al. 1990; Rebenfeld
Circle A
and Cooke 1989). Consequently, the most likely
mechanisms for degradation of geosynthetics in mine
R. (R- and ROOH ROO .
(generation)
waste facilities are mechanical degradation (not ad-
(d)
dressed in this paper), chemical degradation and (b)
oxidative degradation. Loop B
(ROOH
Chemical degradation can occur when geosynthetics . .
RO + OH decomposition)
are exposed to strong chemicals (e.g. acids, bases,
solvents, reactive gases) that alter the polymer by
processes such as swelling, extraction and dissolution. (c)

Oxidative degradation is also a form of chemical RH

ROOH
degradation, but is considered separately owing to its
significance in polymer degradation, even in environ- Figure 1. Chain mechanisms involved in auto-oxidation of
ments where limited oxygen exists (Grassie and Scott polyethylene (adapted from Grassie and Scott 1985)
Geosynthetics International, 2004, 11, No. 2
62
hydroperoxide (ROOH) and creates another free radical
(Fay and King 1994):
ROO
þ RH ! ROOH þ R
ð3Þ
The amount of ROOH generated by Reaction 3 is small,
which results in slow oxidation. When the concentration
of ROOH reaches a critical level, decomposition of
ROOH begins, as shown in Loop B in Figure 1:
ROOH ! RO
þ OH
ð4Þ
Decomposition of ROOH causes a substantial in-
crease in the amount of free radicals, which attack the
polymer chain and accelerate the chain reactions. The
RO
radical reacts with the polymer chain (RH) and
forms more free radicals and alcohol (ROH):
RO
þ RH ! ROH þ R
ð5Þ
The OH
radical reacts with the polymer chain to form
free radicals and water:
OH
þ RH ! H2 O þ R
ð6Þ
Metal ions in mine waste liquids may affect the rate of
these reactions because oxidation of polymers is
accelerated by metals or metallic compounds (Osawa
and Ishizuka 1973). One of the main functions of a
metallic catalyst during oxidation is the breakdown of
hydroperoxides to free radicals. Osawa and Ishizuka
(1973) studied the effects of various metals on oxidative
degradation of polypropylene and found that the
catalytic effect of acid metal salts followed the order
(high to low): Co > Mn > Cu > Fe > V > Ni > Zn >
Al > Mg. Fe, Cu and Zn are commonly found elements
in metallic mine waste liquids, and therefore may
accelerate the degradation of geosynthetics exposed to
these liquids.
2.3. Antioxidants
Antioxidants are added to polymeric materials to inhibit
oxidation and extend the induction period (Al-Malaika
1998; Grassie and Scott 1985). Because geosynthetics are
manufactured at high temperatures (2008C and 2808C),
antioxidants are needed that function at the high
temperatures associated with manufacturing as well as
the lower temperatures associated with in-service appli-
cations. Consequently, manufacturers generally use a
combination of two or more types of antioxidant to
provide overall stability (Fay and King 1994).
The main function of antioxidants is to retard
oxidation by breaking links in the auto-oxidation chains,
shown as a–d in Figure 1. The following antioxidants are
commonly used (operating temperature in parentheses):
hindered phenols (0–3008C), hindered amines (HALS)
(0–1508C), phosphites (150–3008C) and thiosynergists
(0–2008C). Hindered phenols and hindered amines are
primary antioxidants; phosphites and thiosynergists are
secondary antioxidants. Hindered amines are also used
as secondary antioxidants (Fay and King 1994). Primary
antioxidants are also known as ‘chain-breaking antiox-
idants’. They act by either accepting an electron or
donating an electron. Secondary antioxidants are known
Geosynthetics International, 2004, 11, No. 2
Gulec, Edil and Benson
as ‘preventive antioxidants’ because their major function
is to interfere with the formation of free radicals by
decomposing hydroperoxides.
2.4. Depletion of antioxidants
Antioxidants are depleted by chemical reactions to
prevent oxidative degradation of polymers and physical
losses to the surrounding media by volatilisation or by
extraction (Gedde et al. 1994). Volatilisation is not a
major concern for HDPE geomembranes at typical
temperatures in waste containment systems (<608C)
(Hsuan and Koerner 1998). However, extraction can be
significant (Calvert and Billingham 1979). For example,
Smith et al. (1992) found that approximately 75% of the
antioxidants in medium-density polyethylene pipes ex-
posed to water (internally) and air (externally) were lost
by extraction.
Hsuan and Koerner (1995, 1998) studied degradation
and antioxidant depletion of a 1.5-mm-thick HDPE
geomembrane. Four different incubations were used:
water immersion, water immersion with the geomem-
brane loaded to 30% of the yield stress, air immersion,
and one-sided exposure (water above and air below)
under a compressive stress of 260 kPa. Samples were
exposed in water at 55, 65, 75 and 858C and in air at 55,
65, 75, 95 and 1158C. Samples were retrieved periodically
and tested to determine the oxidation induction time
(OIT). The OIT data showed that the depletion rate
increased with increasing exposure temperature, and was
higher for water immersion than for one-sided exposure.
Depletion rates were not reported for air exposure and
water immersion with the geomembrane loaded to 30%
of the yield stress.
The OIT data were used to make lifetime predictions
using the Arrhenius method. The time for antioxidant
depletion at 258C was approximately 40 years for water
immersion and 120 years for water above, air below
exposure. Air exposure and water immersion with the
geomembrane loaded to 30% of the yield stress were not
included in the lifetime predictions. Additional tests
showed that no major changes in density, melt flow index
(MFI) or tensile properties occurred during the 24-
month exposure period (Hsuan and Koerner 1998).
Sangam and Rowe (2002) studied antioxidant deple-
tion in a 2-mm-thick HDPE geomembrane exposed to
synthetic municipal solid waste (MSW) leachate, water
or air at 22, 40, 55, 70 and 858C. The synthetic MSW
leachate had pH 6 and contained the surfactant
IGEPAL CA-720 (5000 mg/l), acetic acid (4000 mg/l),
propionic acid (3000 mg/l), butyric acid (500 mg/l),
HCO7 3 (4876 mg/l), Cl
7
(4414 mg/l), Na+ (1615 ml/g),
+2
Ca (1224 mg/l), and trace metals. OIT of the exposed
geomembrane was measured by standard (Std) and high-
pressure (HP) OIT methods. The antioxidant depletion
rate in the synthetic MSW leachate was 3.8–7.0 times
faster than in air and 2.3–3.2 times faster than in water.
Predictions of the time for antioxidant depletion were
made using the Arrhenius method. The predicted
antioxidant depletion time was at least 40 years at
338C and over 150 years at 138C when exposed to
Effect of acidic mine drainage on the polymer properties of an HDPE geomembrane
MSW leachate in a liner application (Sangam and Rowe
2002).
3. MATERIALS AND METHODS
3.1. Geomembrane
A commercially available 1.5-mm-thick smooth HDPE
geomembrane meeting the criteria in Geosynthetic
Research Institute (GRI) (GRI GM13) was used for
this study. The geomembrane was manufactured as a
single sheet (no co-extrusion) using flat die extrusion.
The unexposed geomembrane had a density of 0.95 g/ml,
MFI = 0.25 g/10 min (mean from four tests per ASTM
D 1238; standard deviation = 0.01 g/10 min), an Std-
OIT of 208 min (average of duplicate tests per ASTM D
3895), and an HP-OIT of 484 min (average of duplicate
tests per ASTM D 5885). The geomembrane consisted of
a blend of polyethylene, carbon black (2%), and an
antioxidant package. Other details of the formulation
were not divulged by the manufacturer.
3.2. Exposure solutions and temperatures
Geomembrane samples were immersed in three different
liquids: synthetic AMD, acidic water, and DI water. The
sample length ranged between 260 and 410 mm and the
width ranged between 460 and 510 mm. Periodically,
samples were removed from the tanks for testing. After
removal, the samples were rinsed with deionised water
and dried with a paper towel. Test specimens were cut
from the samples immediately prior to testing. The
remaining sample was discarded.
A detailed discussion of the solutions is reported by
Gulec (2003). The synthetic AMD contained Fe
(1500 mg/l), Zn (350 mg/l), Cu (35 mg/l), SO4 (4500
mg/l) and Ca (200 mg/l), and was prepared using
FeSO4
7H2O, ZnSO4
7H2O, CuSO4 and CaSO4 along
with H2SO4 to achieve pH 2.1. The acidic water was
prepared using DI water and H2SO4 to pH 2.1, and was
used to distinguish the effects of metals and acidity on
geosynthetic degradation. DI water was used as the
reference solution.
Composition of the synthetic AMD was based on a
review of the composition of a variety of AMDs reported
Table 1. Composition of synthetic AMD and AMDs reported in the literature for metallic mine wastes
Synthetic
Property Units AMD
pH – 2.1
Fe mg/l 1500
Zn mg/l 350
Cu mg/l 35
SO4 mg/l 4500
Ca mg/l 200
Fe : Zn – 4
Zn : Cu – 10
Literature sources for AMD are as follows: Avnesen and Iversen (1997), Christensen and Laake (1996), Crandon
Mining Company (1996), Eidsa et al. (1997), Gauld (1999), Gray (1998), Gusek (1995), Horan (1999), Ing and
Heinrich (1997), Kashir and Yanful (2000).
Geosynthetics International, 2004, 11, No. 2
63
in the literature for metallic mine wastes. This review
identified the most abundant metals, their concentra-
tions, and the relative ratios in AMD (Gulec 2003).
Composition of the synthetic AMD is shown in Table 1
along with the mean, maximum and minimum concen-
trations of key elements in AMDs reported in the
literature. Concentrations of Fe, Zn and Cu were
estimated based on the mean concentrations of Fe, the
mean Fe : Zn ratio, and a Zn : Cu ratio of 10. Concentra-
tions of Ca and SO4 were chosen so that the solution
would have pH around 2 in equilibrium. The geochem-
ical equilibrium speciation model MINTEQA2 (USEPA
1991) was used to estimate the Ca and SO4 concentra-
tions as well as the final composition and pH of the
solution (Gulec 2003).
Insulated stainless steel tanks equipped with heaters
and mixers were used for immersion. The tanks were
maintained at 20, 40 or 608C (one tank for each solution
and each temperature). All metallic items (frames for
hanging samples, heaters, and mixers) were made of
stainless steel to prevent corrosion. Lids were placed on
the tanks to minimise evaporation and to minimise
diffusion of oxygen so as to prevent iron precipitates. To
further limit diffusion of oxygen into the solution, the
headspace was continuously purged with nitrogen and
the surface of the liquid was covered with plastic balls
(diameter = 15 mm). The solution in each tank was also
replaced monthly.
Composition of each solution was monitored (first
weekly and later twice a month) by measuring the pH
and electrical conductivity (EC) and by measuring the
metals’ concentrations using atomic adsorption spectro-
metry. Results of the monitoring showed that the
composition of the solutions remained essentially con-
stant over time. pH was maintained within 2.1  0.15
and EC was maintained within 0.82  0.05 S/m. In
addition, the coefficient of variation for the metals
concentrations was less than 10%. A compilation of all
of the analytical data is reported by Gulec (2003).
3.3. Melt flow index (MFI) test
MFI is a simple method to assess the molecular weight of
polymeric materials and is commonly used as an index of
molecular weight in chemical compatibility studies of
Literature AMDs
Mean Maximum Minimum
2.4 2.8 2.0
1404 5000 198
747 2400 80
183 700 8
9013 20 000 2700
421 460 382
5 13 0
24 206 1
64
geosynthetics (Hsuan and Koerner 1998; Maisonneuve
et al. 1997; Surmann et al. 1995). The MFI protocol
defined by ASTM D 1238 consists in measuring the
amount of molten polymer (1908C) that is extruded
through an orifice in 10 min under a constant load of
2.16 kg. Chain scission reactions, which are one of the
most important consequences of degradation, produce
smaller polymer molecules (Grassie and Scott 1985).
This change in molecular size is reflected as higher MFI.
The MFI tests were conducted by Dickten & Masch
Inc. of Nashotah, WI. Typically one specimen (30 g) was
tested per sample. However, the tests were repeated (a
duplicate test was run) when unusual MFIs were
obtained (e.g. the MFI differed from the mean by 3 or
more standard deviations, a large jump in MFI occurred
of a short period of exposure, or the MFI deviated
appreciably from the trend).
3.4. Fourier transform infrared spectroscopy (FTIR)
Fourier transform infrared spectroscopy (FTIR) is a
spectroscopic method used to detect structural changes
in polymeric materials at the molecular level. A polymer
specimen is subjected to infrared radiation in succes-
sively decreasing frequencies. The amount of infrared
radiation absorbed at each frequency is indicated in a
spectrum. Peaks in the FTIR spectrum generally
correspond to functional groups [e.g. methylene
(–CH2–) or methyl (–CH3–)] that vibrate in a specific
mode at a particular frequency. Polymer structure is
determined by identifying the peaks using catalogues.
Changes observed in the spectrum can be used as
indicators of degradation (Dudzik and Tisinger 1990;
Duquennoi et al. 1995; Maisonneuve et al. 1997; Tisinger
1989).
The FTIR analyses were conducted by Dickten &
Masch Inc. of Nashotah, WI. A small specimen (20–
30 mm square) was cut from an exposed sample for
analysis. The specimen was sealed in a plastic bag and
shipped to the laboratory. The sample was further cut
across its thickness by Dickten & Masch prior to FTIR
analysis. The FTIR analysis was conducted with a
Nicolet Magna FTIR 550 spectrometer equipped with a
micro attenuated total reflectance (ATR) lens and a
Magna 550 infrared (IR) bench.
3.5. Oxidation induction time (OIT) by differential
scanning calorimetry (DSC)
OIT was measured with differential scanning calorimetry
(DSC), a common thermoanalytical method used to
measure OIT (Dudzik and Tisinger 1990; Hsuan and
Koerner 1995, 1998; Maisonneuve et al. 1997; Sangam
and Rowe 2002; Surmann et al. 1995; Tisinger 1989).
Most of the OIT analyses were conducted using the
standard method (Std-OIT) in accordance with ASTM
D 3895. Some were conducted using the high-pressure
method (HP-OIT) in accordance with ASTM D 5885.
Specimens approximately 20–30 mm square were cut
from an exposed sample for OIT testing.
Std-OIT was measured at the University of Wisconsin-
Madison (UW) using a NETZSCH DSC 200 differential
Geosynthetics International, 2004, 11, No. 2
Gulec, Edil and Benson
scanning calorimeter (DSC). The only deviation from
ASTM D 3895 was that the gas flow rate was limited to
35–40 ml/min owing to the capacity of the DSC (D 3895
requires 50 ml/min). A 5–10 mg specimen was heated to
2008C at a rate of 208C/min in a nitrogen atmosphere.
After 2008C was reached, the specimen was maintained
in an isothermal state for 5 min. Then the purge gas was
changed from nitrogen to oxygen, and the change in
enthalpy was recorded. The test was terminated when an
exothermal peak was detected.
To evaluate the importance of the non-standard flow
rate, one sample of unexposed geomembrane was sent to
the Geosynthetic Research Institute (GRI) at Drexel
University for testing at the standard flow rate. Two
replicate tests were conducted on the sample by GRI.
Companion tests were conducted on the same sample at
UW. GRI reported OITs of 204 and 211 min for the
unexposed geomembrane, whereas the OIT determined
at UW was 266 min. Comparison of these tests indicates
that use of the non-standard flow rate resulted in an
overestimate of the Std-OIT by approximately 20%.
Additional tests were conducted with HP-OIT to
verify that the higher temperature employed in the Std-
OIT tests was not outside the effective range of the
antioxidants in the geomembrane (the antioxidants used
in the geomembrane are confidential and were not
divulged by the manufacturer). For example, hindered
amines and thiosynergists will volatilise or degrade in an
Std-OIT test (Hsuan and Guan 1997), which is
conducted at temperatures above their effective range
(0–1508C for hindered amines and 0–2008C for thiosy-
nergists). Standard OIT and HP-OIT tests are similar,
except that relatively high gas pressure and low
temperature are used in HP-OIT tests (specimens are
oxidised at 2008C and 35 kPa in Std-OIT, whereas 1508C
and 3500 kPa are used in HP-OIT). The HP-OIT tests
were conducted in accordance with ASTM D 5885 by
Dickten & Masch, Inc. of Nashotah, WI.
Std-OIT and HP-OIT were both conducted on six
specimens of geomembrane (two unexposed and four
exposed to AMD at 608C for various durations). The
relationship between HP-OIT and Std-OIT for these
specimens is shown in Figure 2. The relationship is
linear, as was observed by Hsuan and Koerner (1998)
and Sangam and Rowe (2002) for other HDPE
geomembranes. A linear relationship between HP-OIT
and Std-OIT indicates that the high temperature in the
Std-OIT test does not destroy the antioxidants, and that
either method can be used to monitor depletion of
antioxidants (Hsuan and Koerner 1998). The linear
relationship also suggests that the antioxidant package
used in the geomembrane is phosphites and phenols,
which have effective temperature ranges of 150–3008C
and 0–3008C respectively (Hsuan and Koerner 1998).
The ratio of Std-OIT to HP-OIT for the unexposed
geomembrane was also calculated and compared with
ratios reported in the literature for HDPE geomem-
branes. The Std-OIT of the unexposed geomembrane
(208 min) measured at GRI was used to preclude
ambiguities caused by the non-standard flow rate used
Effect of acidic mine drainage on the polymer properties of an HDPE geomembrane 65

500 0.30

0.29

0.28
400
High pressure-OIT (min)

Melt flow index (g/10 min)

0.27 m + 2s

0.26 m+s

300 0.25 m

0.24 m−s

0.23 m − 2s
200 20°C
0.22
40°C
0.21
60°C
0.20
100 0 3 6 9 12 15 18 21 24
0 50 100 150 200 250 300
Time (months)
Standard pressure-OIT (min)
(a)
Figure 2. Comparison of OIT of HDPE geomembrane 0.30
determined by high-pressure (ASTM D 5885) and standard
(ASTM D 3895) OIT methods 0.29

0.28

Melt flow index (g/10 min)

0.27 m + 2s
at UW. The ratio for the data in Figure 2 is 2.3, which
0.26 m+s
is comparable to ratios (2.1 and 2.8) reported by Hsuan
and Guan (1997), Hsuan and Koerner (1998) and 0.25 m
Sangam and Rowe (2002) for five HDPE geomembranes 0.24 m−s
with hindered phenols and phosphites as antioxidants.
0.23 m − 2s

0.22 20°C
40°C
4. RESULTS AND DISCUSSION 0.21
60°C
0.20
4.1. Melt flow index (MFI) 0 3 6 9 12 15 18 21 24
Time (months)
MFIs are presented in Figure 3 for the geomembrane
exposed to DI water and the simulated AMD solution. (b)

Each point in Figure 3 corresponds to a single MFI test.
Geomembranes exposed to acidic water were not tested
owing to budget limitations. The mean MFI of the
unexposed geomembrane is shown as the solid horizon-
tal line. One and two standard deviations from the mean
are shown as dashed horizontal lines. For normally
distributed data, one standard deviation from the mean
encompasses 68% of the dispersion in the data, and two
standard deviations from the mean encompass 95% of
the dispersion. MFIs falling within the lines correspond-
ing to two standard deviations generally are consistent
with the scatter associated with the tests on unexposed
geomembrane, and thus are not statistically different
from the MFI for unexposed conditions.
Nearly all of the MFIs for DI water exposure fall
within the lines for two standard deviations, regardless
of the temperature (Figure 3a). The only exception is one
replicate at 208C. This indicates that exposure in DI
water had no statistically significant effect on the bulk
polymer properties over the exposure period. However,
the data do exhibit an upward trend between 12 and 21
months. Thus MFIs outside the normal scatter might
have been obtained had the geomembrane been im-
mersed longer, or if tests were conducted on polymer
close to the surface of the geomembrane (i.e. where
interactions between the solution and polymer may be
greatest). Temperature appears to have little effect on the
Geosynthetics International, 2004, 11, No. 2
Figure 3. MFI against time for geomembrane samples exposed
to: (a) DI water at 20, 40 and 608C; (b) AMD at 20, 40 and 608C
MFI as well. Slightly higher MFIs were obtained at 608C
during the first 12 months, but the MFIs for 208C are
slightly higher than those at 608C after 12 months.
Several MFIs of the geomembrane exposed to AMD
fall above the line corresponding to two standard
deviations above the mean (Figure 3b). However,
duplicate tests on these samples yielded lower MFIs as
well. Thus these large MFI do not necessarily imply that
changes in the polymer occurred due to AMD exposure.
However, the MFIs for AMD exposure generally are
higher than those for exposure to DI water, suggesting
that exposure to AMD caused some alteration of the
polymer.
Analysis of variance (ANOVA) was used to further
evaluate whether any of the treatments had statistically
significant effects on MFI. In ANOVA, the F-statistic is
used to determine whether any of the treatments had a
significantly significant effect (Box et al. 1978). A
comparison is made between the F-statistic computed
using the MFI data for each treatment and a critical
value (Fa) corresponding to a significance level a. If
F < Fa , then the null hypothesis (no difference between
the means of the groups being compared) is accepted.
66 Gulec, Edil and Benson

For this analysis, each of the six treatments (AMD at 20, Table 2. Slopes and p-statistics from linear regression analysis of
40 and 608C and DI water at 20, 40 and 608C) was MFI data
treated as a group, and the MFIs for each treatment Treatment
were compared with each other. The significance level, a,
was set to 0.05, which is the conventional significance Exposure
Exposure temperature
level used in hypothesis testing (Box et al. 1978). The Slope p-value
solution (8C)
ANOVA yielded F = 2.085, whereas F0.05 = 2.43
(F < Fcr). That is, no statistically significant difference DI 20 0.0016 0.047
exists between the mean MFIs corresponding to the six DI 40 0.0005 0.076
DI 60 0.0005 0.185
different treatments (DI water and AMD exposure at 20, AMD 20 0.0010 0.133
40 or 608C). AMD 40 0.0012 0.039
Linear regression of MFI on time was used to evaluate AMD 60 0.0005 0.556
whether a significant temporal trend existed in the MFI
for any of the exposure conditions. In a regression
analysis, the p-statistic is used to determine whether the
slope of the regression (i.e. the temporal trend) is 4.2. FTIR spectra
statistically different from zero. A p-statistic less than Spectra for the geomembrane samples exposed to AMD
the significance level a indicates a statistically significant at 608C for 6, 12 and 18 months are shown in Figure 4
temporal trend. Results of the linear regression are along with the spectrum of the unexposed geomembrane.
presented in Table 2 for a = 0.05. p-statistics higher than AMD exposure at 608C was the most aggressive
0.05 (no temporal trend in MFI) exist for all exposure treatment and therefore was chosen for FTIR testing.
conditions except DI water at 208C and AMD at 408C. Other exposure times and treatments were not tested
However, for each of these two treatments, the last data owing to budget limitations.
point (21 months) is largely responsible for the inference The spectra at 6, 12 and 18 months of AMD exposure
of statistical significance. Thus a definitive inference at 608C (Figures 4b, c and d) are consistent with the
cannot be made that the trends in these two data sets are spectrum of the unexposed geomembrane (Figure 4a),
truly significant. except for one small absorption peak below 1750 cm71

0.8 (a)

0.6

0.4

0.2

0.0
0.8

(b)
0.6

0.4
Absorbance

0.2

0.0
0.8

0.6
(c)
0.4

0.2

0.0

0.4
(d)
0.2

0.0
4000 3000 2000 1000 500

Wave number (cm−1)

Figure 4. FTIR spectra of: (a) unexposed geomembrane; (b) geomembrane exposed to AMD at 608C for 6 months; (c) geomembrane
exposed to AMD at 608C for 12 months; (d) geomembrane exposed to AMD at 608C for 18 months. Arrows indicate extra peaks
observed in geomembrane exposed for 18 months
Geosynthetics International, 2004, 11, No. 2
Effect of acidic mine drainage on the polymer properties of an HDPE geomembrane 67

in the 6-month spectrum and four additional small 300

absorption bands (the most significant of which appear
near 3200 cm71; other bands appear near 1100, 900 and 250
800 cm71) in the 18-month spectrum. The small peak
observed in the 6-month spectrum corresponds to a 200
20°C

Std-OIT (min)
carbonyl (C=O) linkage, which suggests that oxidation 40°C
has occurred in the polymer structure. However, this 60°C
150 80°C
peak was not observed in the longer exposure times (i.e.
12 and 18 months). The extra peak at 6 months may be a
local effect, but a definitive conclusion cannot be made 100

because replicate FTIR analyses were not conducted

owing to budget limitations. Nevertheless, the absence of 50 Fit of first-order degradation
major changes in the spectra suggests that exposure to equation, OITt = OIT0 e−St
AMD at 608C did not significantly change the bulk 0
polymer structure over 18 months. 0 3 6 9 12 15 18 21 24

The small absorption bands observed at 3200, 1100, Exposure time (months)
900 and 800 cm71 in the 18-month spectrum are not (a)
associated with the wavelengths at which polymer
oxidation peaks occur, and are believed to be associated 300

with mixed metal oxides that precipitated on the surface

of the geomembrane during exposure to the AMD. The 250
AMD solution was rich in metals, and precipitation of DI - 60°C
some metal oxides probably occurred despite the meas- 200 Acid - 60°C
Std-OIT (min)

ures taken to prevent the ingress of oxygen. However, AMD - 60°C

types of metal oxides cannot be identified by FTIR. Thus 150
the AMD solution cannot be confirmed as the source of
these peaks.
100

4.3. Oxidation induction time

OITs of the geomembrane exposed to the AMD at 20, 40
and 608C and DI water and acidic water at 608C are
shown in Figure 5. Most of the data in Figure 5 are for
samples exposed at 20, 40 or 608C for up to 21 months.
However, an additional set of samples was exposed at
808C towards the end of the study to assess the effects of
higher temperature. The samples at 808C were only
exposed for 10 weeks.
OIT decreases with exposure time and at a greater rate
at higher temperature (Figure 5a), as has been observed
by others (Hsuan and Guan 1997; Hsuan and Koerner
1995; Sangam and Rowe 2002). Comparison of anti-
oxidant depletion curves for AMD, acidic water and DI
water exposures at 608C in Figure 5b indicate that the
largest and most rapid reductions in OIT occurred in the
AMD, followed by the acidic water, and DI water.
None of the treatments completely depleted the
antioxidants during the exposure period, which is
consistent with the lack of oxidation products in the
FTIR spectra. Moreover, as described in a companion
paper (Gulec et al. 2004), no statistically significant
change in the bulk mechanical properties of the
geomembrane (trapezoid tear strength, puncture
strength, and wide-strip tensile strength) occurred during
the 22 months of exposure. The absence of change in the
mechanical properties is also consistent with incomplete
depletion of the antioxidants and the lack of oxidation
products in the FTIR spectra. Theoretically, degradation
of mechanical properties caused by alterations in the
polymer occurs after the antioxidants are depleted
(Hsuan and Guan 1997).
Geosynthetics International, 2004, 11, No. 2
50 Fit of first-order degradation
equation, OITt = OIT0 e−St
0
0 3 6 9 12 15 18 21 24
Exposure time (months)
(b)
Figure 5. Std-OIT against time for geomembrane exposed to: (a)
AMD at 20, 40 and 608C; (b) AMD, acidic water and DI water
at 608C. OIT0 = OIT of unexposed geomembrane. OITt = OIT
of geomembrane after exposure time t
Graphs of ln OIT against time are shown in Figure 6.
The relationship between ln OIT and time is approxi-
mately linear, suggesting that depletion of the antiox-
idants can be approximated as a first-order process (i.e.
exponential depletion in time). Hsuan and Koerner
(1995) and Sangam and Rowe (2002) also observed first-
order degradation in their antioxidant depletion experi-
ments on HDPE geomembranes. The first-order reaction
rate (S) is the slope of the line of ln OIT against time.
First-order reaction rates (S) for each exposure con-
dition were obtained by linear regression. A summary of
depletion rates and the corresponding coefficients of
determination (R2) is given in Table 3.
Comparison of the depletion rates in Table 3 indicates
that temperature had a significant effect on antioxidant
depletion. For example, the depletion rate for AMD at
608C is 2.2 times higher than that at 408C and 17.6 times
higher than that at 208C. The chemistry of the solution is
also influential. At 608C the depletion rate of AMD is
68 Gulec, Edil and Benson

6.0 effect in a mine waste containment application where

temperature variations are tempered by burial beneath
5.5
the waste.
5.0 The higher depletion rate for AMD exposure relative
to that for acidic water (1.3 times) may be due to the
4.5 metals in the AMD solution. As indicated in Osawa and
ln OIT (min)

First-order degradation
equation: Ishizuka (1973), metals have a catalytic effect on the
4.0
ln OITt = ln OIT0 − St oxidative degradation of polypropylene. However, de-
3.5 pletion of antioxidants by extraction is believed to be the
20°C dominant depletion mechanism in this study owing to
3.0 40°C the limited amount of oxygen in the tanks. The absence
60°C of extensive carbonyl peaks in the FTIR spectra (Figure
2.5
80°C 4) also suggests that oxidation was not appreciable.
2.0 The depletion rates for AMD are shown in Table 4
0 3 6 9 12 15 18 21 24
with those for MSW leachate reported by Sangam and
Exposure time (months) Rowe (2002). At comparable temperatures, the depletion
(a) rate for exposure to MSW leachate is higher than that
for AMD exposure (Table 4). For example, at 208C the
6.0
depletion rate for MSW is 3.7 times higher than the rate
for AMD exposure. That is, MSW leachate appears
5.5 to be more aggressive in depleting antioxidants than
AMD. Inherent in this inference is an assumption that
the geomembrane tested in this study is identical to the
ln OIT (min)

5.0 geomembrane tested by Sangam and Rowe (2002).

The exact properties of both geomembranes are not
known, but the geomembranes have similar density (0.94
4.5
versus 0.95 g/ml), similar Std-to-HP OIT ratios (2.1 to
2.8), and similar OIT depletion rates in water (see
DI - 60°C subsequent discussion). Thus the relative effects of
4.0
Acid - 60°C
exposure to AMD and MSW leachate are believed to
AMD - 60°C
be reliable.
3.5
0 3 6 9 12 15 18 21 24

Exposure time (months) 5. PREDICTIONS OF ANTIOXIDANT

(b)
Figure 6. Logarithm of Std-OIT against time for geomembrane
exposed to: (a) AMD at 20, 40 and 608C; (b) AMD, acidic water
and DI water at 608C
1.8 times higher than the depletion rate for acidic water
and 1.3 times higher than that for DI water. Tempera-
ture had a stronger effect than the solution chemistry
because of the broad range of the temperatures that were
used. However, temperature is expected to have less
DEPLETION TIME
Predictions of antioxidant depletion time were made
using Arrhenius modelling, which is the most widely
used method to predict the lifetime of polymeric
materials (Hsuan and Koerner 1998). The approach is
described in ISO Standard 11346. The Arrhenius
equation is
S ¼ A eðEa =RT Þ ð7Þ
where S is the depletion rate, A is a constant, Ea is the
activation energy, R is the gas constant, and T is

Table 3. Antioxidant depletion rates for HDPE geomembrane in AMD, acidic water and
DI water

Immersion Temperature Depletion rate

medium (8C) (1/months) R2

20 0.0051 0.87
40 0.0480 0.96
AMD
60 0.0906 0.96
80 1.2056 0.99

Acidic water 60 0.0708 0.98

DI water 60 0.0514 0.98

Geosynthetics International, 2004, 11, No. 2

Effect of acidic mine drainage on the polymer properties of an HDPE geomembrane 69

Table 4. Comparison of depletion rates for AMD exposure to depletion rates reported in the literature for
immersion in MSW leachate

Immersion Immersion Depletion rate

Reference medium temperature (8C) (1/months)

22 0.0188
40 0.0886
Sangam and Rowe (2002) MSW leachate
55 0.1504
85 0.4074

20 0.0051
40 0.0480
Current study AMD
60 0.0906
80 1.2056

absolute temperature (8K). The Arrhenius equation can Estimated antioxidant depletion times for water,
also be expressed as AMD and MSW leachate are shown in Figure 8 as a
   function of temperature. At a given temperature, the
Ea 1
ln S ¼ ln A  ð8Þ antioxidant depletion time is longest for exposure to
R T

The depletion rates in Table 3 were used to develop

Arrhenius plots (ln S against 1/T) for exposure to water −1
(Figure 7a) and AMD (Figure 7b). Data reported by Hsuan and Koerner (1997)
Hsuan and Koerner (1995) and Sangam and Rowe Sangam and Rowe (2002)
−2 Current study
(2002) were also used when preparing the Arrhenius plot
for water exposure. Parameters of the Arrhenius
equations were obtained by linear regression of ln S on −3
ln S

1/T, and are shown on the graphs in Figure 7. The data

in the Arrhenius plot for water immersion (Figure 7a)
are remarkably consistent considering that different −4 ln S = 15.79 − 6228(1/T )
HDPE geomembranes were used in each study. The R 2 = 0.99
similarity of these data sets also suggests that the SE = 0.12 min/month
−5
geomembrane tested in this study is similar to the Ea = 51.75 kJ/mol
geomembranes tested by Hsuan and Koerner (1995) and A = 7.2 × 106 min/month
Sangam and Rowe (2002). The geomembrane tested by −6
Hsuan and Koerner (1995) has the same density as the 0.0026 0.0028 0.0030 0.0032 0.0034 0.0036
geomembrane used in this study, which also suggests 1/T (1/°K)
that the geomembranes are similar. (a)
Parameters of the Arrhenius equation for AMD were
1
obtained by linear regression using the data for 20, 40
and 608C. The data point for 808C was not included in
0
the regression because of the short period of exposure
(10 weeks). Nevertheless, the data point at 808C is −1 ln S = 19.16 − 7099(1/T )
consistent with the rest of the data. R 2 = 0.93
The Arrhenius parameters in Figure 7 were used with −2
ln S

the first-order degradation equation to estimate antiox-

idant depletion times for water and AMD exposure at −3
field temperatures between 10 and 358C. The antioxidant
depletion time for MSW leachate was also estimated −4
SE = 0.62 min/month
using the Arrhenius parameters reported by Sangam and Ea = 58.9 kJ/mol
Rowe (2002) (ln A = 13.77 and Ea/R = 43.3 kJ/mol). −5
A = 2.1 × 108 min/month
First-order depletion and a final OIT = 0.5 min (pure
unstabilised HDPE; Hsuan and Koerner 1997) were −6
0.0026 0.0028 0.0030 0.0032 0.0034 0.0036
assumed. The initial OIT was set at 100 min, which falls
1/T (1/°K)
within the range of the initial OITs for HDPE
geomembranes reported by Hsuan and Guan (1997) (b)

(112–156 min), Hsuan and Koerner (1997, 1998) Figure 7. Arrhenius plot of antioxidant depletion for: (a) water;
(80.5 min), and Sangam and Rowe (2002) (133 min). (b) AMD exposure. Data for water are from tests conducted by
The antioxidant depletion rates were assumed to be Hsuan and Koerner (1997), Sangam and Rowe (2002), and
independent of the initial OIT. current study. SE = standard error
Geosynthetics International, 2004, 11, No. 2
70 Gulec, Edil and Benson

250 or both sides. These depletion times can be considered as

conservative estimates of the lifetime of the geomem-
brane. The actual lifetime will likely be longer because
Antioxidant depletion time (yr)

200
150
Water
100
AMD
50
MSW
leachate
0 exposure. Thus depletion rates for one-sided exposure
5 10 15 20 25
Field temperature (°C)
Figure 8. Antioxidant depletion time against field temperature of
geomembrane exposed to water, synthetic MSW leachate and
synthetic AMD. Curve for water is based on the collective data
presented in Figure 7a. Curve for MSW leachate is based on
Sangam and Rowe (2002). Curve for AMD is based on data from
the current study
water and shortest for exposure to MSW. The lifetime
for AMD falls between those for water and MSW
leachate. For typical environment temperatures at
depth (15–258C, Lundy 1981), the antioxidant depletion
time ranges between 45 and 105 years for AMD
exposure.
6. PRACTICAL IMPLICATIONS
Estimates of the antioxidant depletion times of an
HDPE geomembrane in a mine waste containment
facility were made assuming that the leachate is
comparable to the synthetic AMD used in this study,
the field temperature is between 15 and 258C (Lundy
1981), and the geomembrane is exposed to AMD on
only one side (i.e. the interior of the containment facility)
the induction time and degradation period have not been
included (Hsuan and Koerner 1998).
No one-sided exposure tests were conducted in this
study. Therefore the effect of one-sided exposure relative
to complete immersion was estimated by reviewing data
reported by Hsuan and Koerner (1995) and Sangam and
Rowe (2002). A comparison of depletion rates for
immersion and one-sided exposure to water is given in
Table 5. Sangam and Rowe (2002) report rates for
immersion in air and water, but not for one-sided
30 35 40 based on the data by Sangam and Rowe (2002) were
computed by averaging the depletion rates for liquid and
air immersion.
The ratio of the depletion rates for one-sided exposure
to immersion in water ranges from 0.28 to 0.34 for the
data by Hsuan and Koerner (1997) and from 0.73 to 0.74
for the data by Sangam and Rowe (2002). The ratios
obtained using the data from Hsuan and Koerner (1997)
are believed to be more representative because they are
based on actual one-sided tests rather than on the
average of ratios from air and liquid immersions. Thus
the ratios for the data by Hsuan and Koerner (1995)
were used in the assessment of depletion time.
Estimated antioxidant depletion times for HDPE
geomembranes exposed to AMD in the field are shown
in Table 6. The calculations in Table 6 were made
assuming first-order depletion for initial OITs of 100
and 200 min for one-sided exposure and immersion.
Depletion rates for one-sided exposure were calcu-
lated by multiplying depletion rates for immersion in
AMD by the ratios for the data from Hsuan and
Koerner (1995) in Table 5 at the corresponding
temperatures.
The antioxidant depletion lifetimes in Table 6 range
from 46 to 426 years depending on the field temperature,
the initial OIT, and the exposure condition. These

Table 5. Comparison of depletion rates reported for liquid immersion and one-sided exposure

Assumed field Depletion rate

Reference Exposure method temperature(a) (C) (1/months) One-sided/immersion ratio
15 0.005 29 158C 0.28
Water immersion 20 0.007 20
Hsuan and Koerner 25 0.009 69
(1995) 208C 0.33
Water above/air below 15 0.001 50
(under 260 kPa 20 0.002 36
258C 0.34
compression) 25 0.003 29

15 0.002 95 158C 0.73

Water immersion 20 0.004 28
Sangam and Rowe 25 0.006 14
(2002) 208C 0.74
15 0.002 16
Water–air average 20 0.003 15
25 0.004 53 258C 0.74

(a)
Not an immersion temperature. The depletion rates are calculated by extrapolation.

Geosynthetics International, 2004, 11, No. 2

Effect of acidic mine drainage on the polymer properties of an HDPE geomembrane
Table 6. Expected antioxidant lifetime in years for polyethylene geomembrane exposed to AMD in the field
Field temperature
(8C)
100 min
Immersion
15 106
20 69
25 46 136
Note: One-sided exposure computed by reducing depletion rate using ratios from Hsuan and Koerner (1995), which are in Table 5.
estimates consider only antioxidant depletion time.
Therefore actual degradation of the engineering proper-
ties may take longer than reported in Table 6.
If one-sided exposure is assumed, then the estimated
depletion time ranges between 136 and 377 years for an
initial OIT of 100 min and between 154 and 426 years for
an initial OIT of 200 min. These depletion times are
longer than those commonly assumed in design (e.g. 30
to 150 years), but are shorter than the reactive lifespan of
many mine wastes. For example, Blowes and Jambor
(1990) estimate that sulfide oxidation contributing to
AMD will continue at the Waite Amulet tailings
impoundment in Quebec, Canada, for more than 500
years.
7. SUMMARY AND CONCLUSIONS
This paper describes a study that was conducted to
evaluate how exposure to acid mine drainage (AMD)
from metallic mine wastes affects the polymer properties
of HDPE geomembranes. Geomembrane samples were
immersed in synthetic AMD, acidic water, and DI water
in tanks maintained at 20, 40 and 608C. Periodically,
samples of each geosynthetic were removed from the
solution and tested to determine the melt flow index
(MFI), Fourier transform infrared spectrum (FTIR),
and oxidation induction time (OIT).
Results of the MFI and FTIR tests showed that
exposure to AMD or DI water had little effect on the
polymer properties. No consistent changes in the
polymer structure were observed. However, the MFI
did appear to increase gradually, and greater changes
might have been observed had the geomembrane been
immersed longer.
OIT decreased with exposure time for all exposure
conditions and approximately followed a first-order
depletion rate. The depletion rate also increased as the
temperature increased, and was greatest for exposure to
AMD. Comparison of antioxidant depletion rates for
AMD exposure with those reported for MSW leachate
indicates that the depletion rate for exposure to MSW
leachate exposure is two to four times higher than the
rate for AMD exposure.
An analysis was conducted to estimate the antioxidant
depletion time of HDPE geomembranes in mine waste
containment facilities. The antioxidant depletion time
ranged from 46 to 426 years, depending on the field
Geosynthetics International, 2004, 11, No. 2
71
Initial OIT
200 min
One-sided exposure Immersion One-sided exposure
377 119 426
210 78 238
52 154
temperature, the initial OIT, and exposure condition. If
one-side exposure is assumed, then the antioxidant
depletion time should exceed 136 years. This antioxidant
lifetime is greater than those commonly assumed during
design, but is shorter than the reactive lifetime of some
metallic mine wastes. However, these lifetime estimates
consider only the antioxidant depletion time and do not
account for the induction time and time required for
degradation of engineering properties.
ACKNOWLEDGEMENTS
This study was sponsored by the State of Wisconsin’s
Groundwater Research Advisory Council, which is
administered through the Water Resources Institute at
the University of Wisconsin-Madison. The geomem-
brane used in this study was donated by GSE. Y. G.
Hsuan of Drexel University provided the OIT tests
conducted at the Geosynthetic Research Institute. M.
Fredrickson and B. Trzebiatowski are acknowledged for
their help throughout the study.
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