Geosynthetics International, 2004, 11, No.

Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane

S. B. Gulec1, T. B. Edil2 and C. H. Benson3
Senior Sta Engineer, GeoSyntec Consultants, 1100 Lake Hearn Driver, Suite 200, Atlanta, GA 30342, USA, Telephone: +1 404 705 9500, Telefax: +1 404 705 9400, Email: 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 eects 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 ow index (MFI), polymer structure (as determined by Fourier transform infrared spectroscopy, or FTIR), and oxidation induction time. Only modest eects 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 rst-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 eld 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). Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane. Geosynthetics International, 11, No. 2, 6072
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1. INTRODUCTION
Acid mine drainage (AMD), the leachate from waste rock and tailings from mining and beneciation of sulde-rich ores, poses a threat to groundwater and surface water at mine sites worldwide. AMD is formed when sulde-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 landlls (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 geomembranes, geotextiles and geocomposite drainage layers, to
1072-6349 # 2004 Thomas Telford Ltd

prevent leakage and to collect leachate for treatment. Because geosynthetics play a pivotal role in the eectiveness of these waste containment facilities, the longterm 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 aect geosynthetic materials (Gulec 2003). This paper describes part of a study conducted to evaluate how exposure to AMD from metallic mine wastes aects 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 aected their bulk properties. Eects on the polymer properties of the geomembrane are described in this paper. Polymer properties were investigated because the durability of
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Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane geosynthetic materials depends largely on the composition of the polymers from which they are made as well as on conditions during the fabrication process (Cassidy et al. 1991). Eects of exposure on the mechanical (trapezoid tear strength, puncture strength, and widestrip tensile strength) and hydraulic (permittivity, transmissivity) properties of the geosynthetics are described by Gulec et al. (2004). In general, no statistically signicant changes in the mechanical or hydraulic properties of the geosynthetics occurred during the 22-month exposure period.

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1985; Klemchuk 2002). Oxidative attack has been reported to have particularly severe impact on polyolens (e.g. polyethylene and polypropylene) (Horrocks et al. 1997; Sangam and Rowe 2002). 2.2. Oxidation of polyethylene Oxidation of polyethylene is an auto-accelerating process, meaning that the rate is slow at rst, but gradually accelerates. The period before oxidation accelerates (and measurable degradation takes place) is called the induction period (Hsuan and Koerner 1998). When polymer degradation due to auto-oxidation chain reactions becomes severe, alteration of the physical and mechanical properties of polymers occurs (Hsuan and Koerner 1998). Oxidation of polyethylene is caused by an autooxidation chain mechanism that involves two interacting cyclical processes, shown as Circle A and Loop B in Figure 1. Circle A consists in the formation of hydroperoxide (ROOH) and free radicals, and Loop B consists in decomposition of the hydroperoxide to form more free radicals (Grassie and Scott 1985). The degradation reactions start with generation of a free radical (R) (any species that contains one or more unpaired electrons, which make the species reactive) from the polymer chain (RH): RH ! R H 1

2. BACKGROUND
2.1. Degradation of geosynthetics The following mechanisms can degrade geosynthetics, depending on the nature of exposure and the type of polymer: UV light, radiation, elevated temperatures, chemical disintegration, mechanical damage and oxidation (Haxo and Nelson 1984; Koerner et al. 1990). Degradation generally begins as changes in the polymer structure and eventually is manifested as changes in engineering properties (e.g. mechanical and hydraulic properties) of geosynthetics (Hsuan and Koerner 1998). Common changes in the polymer include embrittlement, reduction or gain in molecular weight, generation of free radicals, loss of additives and plasticizers, and impairment of transparency (Kulshreshtha 1992). Identication of a single dominant degradation mechanism for geosynthetics used in mine waste liner systems is not possible because, in most cases, more than one of the listed degradation mechanisms is encountered. However, some of the aforementioned degradation mechanisms are unlikely for mine waste applications. Geosynthetics are buried in liner applications, which eliminates UV degradation except during construction. Radiation generally is not important because radioactive materials generally do not exist in appreciable quantities in most metallic mine wastes (except those associated with uranium mining). Thermal degradation (i.e. degradation of a polymer at elevated temperatures without the involvement of another compound) is negligible at common environmental temperatures (Schnabel 1981) except near seams, and microbiological attack is unlikely owing to the high molecular weight of polymer resins used in geosynthetics (Koerner et al. 1990; Rebenfeld and Cooke 1989). Consequently, the most likely mechanisms for degradation of geosynthetics in mine waste facilities are mechanical degradation (not addressed in this paper), chemical degradation and oxidative degradation. Chemical degradation can occur when geosynthetics are exposed to strong chemicals (e.g. acids, bases, solvents, reactive gases) that alter the polymer by processes such as swelling, extraction and dissolution. Oxidative degradation is also a form of chemical degradation, but is considered separately owing to its signicance in polymer degradation, even in environments where limited oxygen exists (Grassie and Scott

Catalysts, heat or UV light can initiate chain scission in the polymer, generating free radical species (Fay and King 1994). After the free radical is generated, it reacts with oxygen and forms peroxy radical (ROO) (Circle A): R O2 ! ROO 2

The peroxy radical (ROO) then abstracts a hydrogen atom from the surrounding polymer chain to form

O2 Start of reactions RH (Polymer chain) (a)

R (d)

Circle A (R- and ROOH (generation)

ROO

(b) Loop B (ROOH decomposition)

RO + OH

. .

(c) ROOH RH

Figure 1. Chain mechanisms involved in auto-oxidation of polyethylene (adapted from Grassie and Scott 1985)

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62 hydroperoxide (ROOH) and creates another free radical (Fay and King 1994): ROO RH ! ROOH R 3

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 signicant (Calvert and Billingham 1979). For example, Smith et al. (1992) found that approximately 75% of the antioxidants in medium-density polyethylene pipes exposed 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 dierent incubations were used: water immersion, water immersion with the geomembrane 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 ow index (MFI) or tensile properties occurred during the 24month exposure period (Hsuan and Koerner 1998). Sangam and Rowe (2002) studied antioxidant depletion 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), 7 HCO7 (4414 mg/l), Na+ (1615 ml/g), 3 (4876 mg/l), Cl +2 Ca (1224 mg/l), and trace metals. OIT of the exposed geomembrane was measured by standard (Std) and highpressure (HP) OIT methods. The antioxidant depletion rate in the synthetic MSW leachate was 3.87.0 times faster than in air and 2.33.2 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

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 OH 4

Decomposition of ROOH causes a substantial increase 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 RH ! ROH R 5

The OH radical reacts with the polymer chain to form free radicals and water: OH RH ! H2 O R 6

Metal ions in mine waste liquids may aect 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 eects of various metals on oxidative degradation of polypropylene and found that the catalytic eect 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 applications. 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 ad in Figure 1. The following antioxidants are commonly used (operating temperature in parentheses): hindered phenols (03008C), hindered amines (HALS) (01508C), phosphites (1503008C) and thiosynergists (02008C). 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 antioxidants. They act by either accepting an electron or donating an electron. Secondary antioxidants are known

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Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane MSW leachate in a liner application (Sangam and Rowe 2002).

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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 at 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 StdOIT 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 dierent 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 FeSO47H2O, ZnSO47H2O, 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 eects 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

in the literature for metallic mine wastes. This review identied the most abundant metals, their concentrations, 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 concentrations 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. Concentrations of Ca and SO4 were chosen so that the solution would have pH around 2 in equilibrium. The geochemical equilibrium speciation model MINTEQA2 (USEPA 1991) was used to estimate the Ca and SO4 concentrations as well as the nal 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 diusion of oxygen so as to prevent iron precipitates. To further limit diusion 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 (rst weekly and later twice a month) by measuring the pH and electrical conductivity (EC) and by measuring the metals concentrations using atomic adsorption spectrometry. Results of the monitoring showed that the composition of the solutions remained essentially constant over time. pH was maintained within 2.1 0.15 and EC was maintained within 0.82 0.05 S/m. In addition, the coecient 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 ow 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

Table 1. Composition of synthetic AMD and AMDs reported in the literature for metallic mine wastes
Literature AMDs Property pH Fe Zn Cu SO4 Ca Fe : Zn Zn : Cu Units mg/l mg/l mg/l mg/l mg/l Synthetic AMD 2.1 1500 350 35 4500 200 4 10 Mean 2.4 1404 747 183 9013 421 5 24 Maximum 2.8 5000 2400 700 20 000 460 13 206 Minimum 2.0 198 80 8 2700 382 0 1

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).

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64 geosynthetics (Hsuan and Koerner 1998; Maisonneuve et al. 1997; Surmann et al. 1995). The MFI protocol dened by ASTM D 1238 consists in measuring the amount of molten polymer (1908C) that is extruded through an orice 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 reected 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 diered 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 successively 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 specic 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 reectance (ATR) lens and a Magna 550 infrared (IR) bench. 3.5. Oxidation induction time (OIT) by dierential scanning calorimetry (DSC) OIT was measured with dierential 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 2030 mm square were cut from an exposed sample for OIT testing. Std-OIT was measured at the University of WisconsinMadison (UW) using a NETZSCH DSC 200 dierential

Gulec, Edil and Benson scanning calorimeter (DSC). The only deviation from ASTM D 3895 was that the gas ow rate was limited to 3540 ml/min owing to the capacity of the DSC (D 3895 requires 50 ml/min). A 510 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 ow rate, one sample of unexposed geomembrane was sent to the Geosynthetic Research Institute (GRI) at Drexel University for testing at the standard ow 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 ow 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 StdOIT tests was not outside the eective range of the antioxidants in the geomembrane (the antioxidants used in the geomembrane are condential 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 eective range (01508C for hindered amines and 02008C for thiosynergists). 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 eective temperature ranges of 1503008C and 03008C 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 geomembranes. The Std-OIT of the unexposed geomembrane (208 min) measured at GRI was used to preclude ambiguities caused by the non-standard ow rate used

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Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane

500

65

0.30 0.29 0.28

High pressure-OIT (min)

Melt flow index (g/10 min)

400

0.27 0.26 0.25 0.24 0.23 0.22 0.21

20C 40C 60C

m + 2s m+s m ms m 2s

300

200

100 0 50 100 150 200 250 300 Standard pressure-OIT (min)

0.20 0 3 6 9 12
(a)

15

18

21

24

Time (months)

Figure 2. Comparison of OIT of HDPE geomembrane determined by high-pressure (ASTM D 5885) and standard (ASTM D 3895) OIT methods
Melt flow index (g/10 min)

0.30 0.29 0.28

at UW. The ratio for the data in Figure 2 is 2.3, which is comparable to ratios (2.1 and 2.8) reported by Hsuan and Guan (1997), Hsuan and Koerner (1998) and Sangam and Rowe (2002) for ve HDPE geomembranes with hindered phenols and phosphites as antioxidants.

0.27 0.26 0.25 0.24 0.23 0.22

20C 40C 60C

m + 2s m+s m ms m 2s

4. RESULTS AND DISCUSSION

4.1. Melt ow index (MFI) MFIs are presented in Figure 3 for the geomembrane exposed to DI water and the simulated AMD solution. 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 horizontal 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 corresponding to two standard deviations generally are consistent with the scatter associated with the tests on unexposed geomembrane, and thus are not statistically dierent 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 signicant eect 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 immersed 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 eect on the

0.21 0.20 0 3 6 9 12 15 Time (months)

(b)

18

21

24

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 rst 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 signicant eects on MFI. In ANOVA, the F-statistic is used to determine whether any of the treatments had a signicantly signicant eect (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 signicance level a. If F < Fa , then the null hypothesis (no dierence between the means of the groups being compared) is accepted.

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66 For this analysis, each of the six treatments (AMD at 20, 40 and 608C and DI water at 20, 40 and 608C) was treated as a group, and the MFIs for each treatment were compared with each other. The signicance level, a, was set to 0.05, which is the conventional signicance level used in hypothesis testing (Box et al. 1978). The ANOVA yielded F = 2.085, whereas F0.05 = 2.43 (F < Fcr). That is, no statistically signicant dierence exists between the mean MFIs corresponding to the six dierent treatments (DI water and AMD exposure at 20, 40 or 608C). Linear regression of MFI on time was used to evaluate whether a signicant 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 statistically dierent from zero. A p-statistic less than the signicance level a indicates a statistically signicant temporal trend. Results of the linear regression are presented in Table 2 for a = 0.05. p-statistics higher than 0.05 (no temporal trend in MFI) exist for all exposure conditions except DI water at 208C and AMD at 408C. However, for each of these two treatments, the last data point (21 months) is largely responsible for the inference of statistical signicance. Thus a denitive inference cannot be made that the trends in these two data sets are truly signicant.

Gulec, Edil and Benson

Table 2. Slopes and p-statistics from linear regression analysis of MFI data
Treatment Exposure temperature (8C) 20 40 60 20 40 60

Exposure solution DI DI DI AMD AMD AMD

Slope 0.0016 0.0005 0.0005 0.0010 0.0012 0.0005

p-value 0.047 0.076 0.185 0.133 0.039 0.556

4.2. FTIR spectra Spectra for the geomembrane samples exposed to AMD at 608C for 6, 12 and 18 months are shown in Figure 4 along with the spectrum of the unexposed geomembrane. AMD exposure at 608C was the most aggressive treatment and therefore was chosen for FTIR testing. Other exposure times and treatments were not tested owing to budget limitations. The spectra at 6, 12 and 18 months of AMD exposure at 608C (Figures 4b, c and d) are consistent with the spectrum of the unexposed geomembrane (Figure 4a), except for one small absorption peak below 1750 cm71

0.8 0.6 0.4 0.2 0.0 0.8 0.6 0.4 Absorbance 0.2 0.0 0.8 0.6

(a)

(b)

(c) 0.4 0.2 0.0 0.4 (d) 0.2 0.0 4000

3000

2000 Wave number (cm1)

1000

500

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

Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane in the 6-month spectrum and four additional small absorption bands (the most signicant of which appear near 3200 cm71; other bands appear near 1100, 900 and 800 cm71) in the 18-month spectrum. The small peak observed in the 6-month spectrum corresponds to a carbonyl (C=O) linkage, which suggests that oxidation has occurred in the polymer structure. However, this 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 eect, but a denitive conclusion cannot be made because replicate FTIR analyses were not conducted owing to budget limitations. Nevertheless, the absence of major changes in the spectra suggests that exposure to AMD at 608C did not signicantly change the bulk polymer structure over 18 months. The small absorption bands observed at 3200, 1100, 900 and 800 cm71 in the 18-month spectrum are not associated with the wavelengths at which polymer oxidation peaks occur, and are believed to be associated with mixed metal oxides that precipitated on the surface of the geomembrane during exposure to the AMD. The AMD solution was rich in metals, and precipitation of some metal oxides probably occurred despite the measures taken to prevent the ingress of oxygen. However, types of metal oxides cannot be identied by FTIR. Thus the AMD solution cannot be conrmed as the source of these peaks. 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 eects 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 antioxidant 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 signicant 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).
50 Fit of first-order degradation equation, OITt = OIT0 eSt 300

67

250 20C 40C 60C 150 80C

Std-OIT (min)

200

100

50

Fit of first-order degradation equation, OITt = OIT0 eSt 0 3 6 9 12 15 18 21 24

0 Exposure time (months) (a) 300

250 DI - 60C 200 Std-OIT (min) Acid - 60C AMD - 60C 150

100

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 approximately linear, suggesting that depletion of the antioxidants can be approximated as a rst-order process (i.e. exponential depletion in time). Hsuan and Koerner (1995) and Sangam and Rowe (2002) also observed rstorder degradation in their antioxidant depletion experiments on HDPE geomembranes. The rst-order reaction rate (S) is the slope of the line of ln OIT against time. First-order reaction rates (S) for each exposure condition were obtained by linear regression. A summary of depletion rates and the corresponding coecients of determination (R2) is given in Table 3. Comparison of the depletion rates in Table 3 indicates that temperature had a signicant eect 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 inuential. At 608C the depletion rate of AMD is

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6.0 5.5 5.0 ln OIT (min) 4.5 4.0 3.5 20C 3.0 2.5 2.0 40C 60C 80C 0 3 6 9 12 15 18 21 24 First-order degradation equation: ln OITt = ln OIT0 St

Gulec, Edil and Benson eect in a mine waste containment application where temperature variations are tempered by burial beneath the waste. The higher depletion rate for AMD exposure relative to that for acidic water (1.3 times) may be due to the metals in the AMD solution. As indicated in Osawa and Ishizuka (1973), metals have a catalytic eect on the oxidative degradation of polypropylene. However, depletion of antioxidants by extraction is believed to be the dominant depletion mechanism in this study owing to the limited amount of oxygen in the tanks. The absence of extensive carbonyl peaks in the FTIR spectra (Figure 4) also suggests that oxidation was not appreciable. The depletion rates for AMD are shown in Table 4 with those for MSW leachate reported by Sangam and Rowe (2002). At comparable temperatures, the depletion rate for exposure to MSW leachate is higher than that for AMD exposure (Table 4). For example, at 208C the depletion rate for MSW is 3.7 times higher than the rate for AMD exposure. That is, MSW leachate appears 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 geomembrane tested by Sangam and Rowe (2002). The exact properties of both geomembranes are not known, but the geomembranes have similar density (0.94 versus 0.95 g/ml), similar Std-to-HP OIT ratios (2.1 to 2.8), and similar OIT depletion rates in water (see subsequent discussion). Thus the relative eects of exposure to AMD and MSW leachate are believed to be reliable.

Exposure time (months) (a) 6.0

5.5

ln OIT (min)

5.0

4.5

4.0

DI - 60C Acid - 60C AMD - 60C

3.5 0 3 6 9 12 15 18 21 24

Exposure time (months) (b)

5. PREDICTIONS OF ANTIOXIDANT 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 A eEa =RT 7

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. Temperature had a stronger eect than the solution chemistry because of the broad range of the temperatures that were used. However, temperature is expected to have less

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 medium Temperature (8C) 20 40 60 80 60 60 Depletion rate (1/months) 0.0051 0.0480 0.0906 1.2056 0.0708 0.0514 R2 0.87 0.96 0.96 0.99 0.98 0.98

AMD

Acidic water DI water

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Eect of acidic mine drainage on the polymer properties of an HDPE geomembrane

Table 4. Comparison of depletion rates for AMD exposure to depletion rates reported in the literature for immersion in MSW leachate
Reference Immersion medium Immersion temperature (8C) 22 40 55 85 20 40 60 80 Depletion rate (1/months) 0.0188 0.0886 0.1504 0.4074 0.0051 0.0480 0.0906 1.2056

69

Sangam and Rowe (2002)

MSW leachate

Current study

AMD

absolute temperature (8K). The Arrhenius equation can also be expressed as    Ea 1 ln S ln A 8 T R The depletion rates in Table 3 were used to develop Arrhenius plots (ln S against 1/T) for exposure to water (Figure 7a) and AMD (Figure 7b). Data reported by Hsuan and Koerner (1995) and Sangam and Rowe (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 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 dierent HDPE geomembranes were used in each study. The similarity of these data sets also suggests that the geomembrane tested in this study is similar to the geomembranes tested by Hsuan and Koerner (1995) and Sangam and Rowe (2002). The geomembrane tested by Hsuan and Koerner (1995) has the same density as the geomembrane used in this study, which also suggests that the geomembranes are similar. Parameters of the Arrhenius equation for AMD were obtained by linear regression using the data for 20, 40 and 608C. The data point for 808C was not included in the regression because of the short period of exposure (10 weeks). Nevertheless, the data point at 808C is consistent with the rest of the data. The Arrhenius parameters in Figure 7 were used with the rst-order degradation equation to estimate antioxidant depletion times for water and AMD exposure at eld temperatures between 10 and 358C. The antioxidant depletion time for MSW leachate was also estimated using the Arrhenius parameters reported by Sangam and Rowe (2002) (ln A = 13.77 and Ea/R = 43.3 kJ/mol). First-order depletion and a nal OIT = 0.5 min (pure unstabilised HDPE; Hsuan and Koerner 1997) were assumed. The initial OIT was set at 100 min, which falls within the range of the initial OITs for HDPE geomembranes reported by Hsuan and Guan (1997) (112156 min), Hsuan and Koerner (1997, 1998) (80.5 min), and Sangam and Rowe (2002) (133 min). The antioxidant depletion rates were assumed to be independent of the initial OIT.

Estimated antioxidant depletion times for water, AMD and MSW leachate are shown in Figure 8 as a function of temperature. At a given temperature, the antioxidant depletion time is longest for exposure to

1 Hsuan and Koerner (1997) Sangam and Rowe (2002) Current study

ln S

ln S = 15.79 6228(1/T ) R 2 = 0.99 SE = 0.12 min/month Ea = 51.75 kJ/mol A = 7.2 106 min/month

6 0.0026

0.0028

0.0030

0.0032 1/T (1/K) (a)

0.0034

0.0036

1 0 1 2 3 4 5 6 0.0026 ln S = 19.16 7099(1/T ) R 2 = 0.93 ln S

SE = 0.62 min/month Ea = 58.9 kJ/mol A = 2.1 108 min/month

0.0028

0.0030

0.0032 1/T (1/K) (b)

0.0034

0.0036

Figure 7. Arrhenius plot of antioxidant depletion for: (a) water; (b) AMD exposure. Data for water are from tests conducted by Hsuan and Koerner (1997), Sangam and Rowe (2002), and current study. SE = standard error

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250

Gulec, Edil and Benson or both sides. These depletion times can be considered as conservative estimates of the lifetime of the geomembrane. The actual lifetime will likely be longer because 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 eect 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 exposure. Thus depletion rates for one-sided exposure 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 eld are shown in Table 6. The calculations in Table 6 were made assuming rst-order depletion for initial OITs of 100 and 200 min for one-sided exposure and immersion. Depletion rates for one-sided exposure were calculated 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 eld temperature, the initial OIT, and the exposure condition. These

Antioxidant depletion time (yr)

200

150 Water 100 AMD

50 MSW leachate 0 5 10 15 20 25 30 35 40 Field temperature (C)

Figure 8. Antioxidant depletion time against eld 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 (15258C, 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 eld 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)

Table 5. Comparison of depletion rates reported for liquid immersion and one-sided exposure
Reference Exposure method Water immersion Hsuan and Koerner (1995) Assumed eld temperature(a) (C) 15 20 25 15 20 25 15 20 25 15 20 25 Depletion rate (1/months) 0.005 29 0.007 20 0.009 69 0.001 50 0.002 36 0.003 29 0.002 95 0.004 28 0.006 14 0.002 16 0.003 15 0.004 53 One-sided/immersion ratio 158C 208C Water above/air below (under 260 kPa compression) 258C 158C 0.28 0.33 0.34 0.73

Water immersion Sangam and Rowe (2002) Waterair average

(a)

208C 258C

0.74 0.74

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

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Eect 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 eld
Field temperature (8C) 100 min Immersion 15 20 25 46 106 69 136 One-sided exposure 377 210 52 Immersion 119 78 154 Initial OIT 200 min

71

One-sided exposure 426 238

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 properties 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 sulde oxidation contributing to AMD will continue at the Waite Amulet tailings impoundment in Quebec, Canada, for more than 500 years.

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 Wisconsins Groundwater Research Advisory Council, which is administered through the Water Resources Institute at the University of Wisconsin-Madison. The geomembrane 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.

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 aects 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 ow 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 eect 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 rst-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 eld

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