Permeation of Organics through Linear Low Density Polyethylene Geomembranes under Mechanical Deformation

The effect of mechanical deformation on the permeation of methylene chloride (MEC), trichloroethylene (TCE) as well as mixtures thereof through linear low-density polyethylene (LLDPE) geomembranes was studied using a new experimental technique. A total of fifty experimental conditions involving five different deformations, five different concentrations and two types of LLDPE geomembranes were evaluated following a full factorial experimental design. Mixtures of TCE and MEC (0.66, 0.50, and 0.34 volumetric fraction) were tested through geomembranes elongated uniaxially (10% and 20%) as well as in the biaxial mode (10%×10%?and?20%×20%). The breakthrough times for the permeation of TCE and MEC decreased with elongation for both types of geomembranes. A reduction in breakthrough times between 38 and 45% was observed for the permeation of MEC and TCE though geomembranes elongated 20%×20% in the biaxial mode compared to the nonelongated specimens. Evidence of stress-enhanced transport was also observed as the steady-state permeation rates of MEC increased between 200 and 300% where geomembranes were elongated 20%×20% in the biaxial mode compared to the nonelongated samples. Enhanced transport of MEC was also noted during the permeation of the MEC–TCE mixtures.     

Permeation of BTEX through Unaged and Aged HDPE Geomembranes

The effects of aging of high-density polyethylene (HDPE) geomembranes on the diffusion and partitioning of a group of volatile organic compounds (VOCs) are examined. Two different 1.5?mm thick HDPE geomembranes were aged in the laboratory at 85°C by immersing in a synthetic leachate for up to 32?months. The results of partitioning and diffusion tests performed at room temperature on both unaged and aged geomembranes using a dilute aqueous solution containing four VOCs commonly found in landfill leachates [benzene, toluene, ethylbenzene, and xylenes (BTEX)] are reported. The diffusion and partitioning coefficients decreased with increased aging. The calculated permeation coefficients decreased by 36–62% after aging the geomembrane for about 10–32?months. This decrease in diffusion, partitioning, and permeation coefficients is related to the increase in geomembrane crystallinity during aging. A relationship between partitioning, diffusion, and permeation coefficients with the geomembrane crystallinity is established and could potentially be used to evaluate the migration of VOCs through HDPE geomembranes. Aging of HDPE geomembrane did not increase diffusive transport of organic contaminants.     

Estimation of Mass Transport Parameters of Organic Compounds through High Density Polyethylene Geomembranes Using a Modifield Double-Compartment Apparatus

A modified double-compartment apparatus (MDCA) is used to estimate mass transport parameters of organic compounds through high density polyethylene (HDPE) geomembranes and to investigate the effects of aging and external tension of HDPE geomembranes on the mass transport of organic compounds. A developed one-dimensional partition–diffusion mass transport model successfully explains the mass transport of the organic compounds through the HDPE geomembranes in a dilute aqueous solution–geomembrane system. Similar to batch immersion tests, the HDPE–water partition coefficient (KHDPE–W) values of organic compounds are found to have close relationships with the octanol–water partition coefficient and the aqueous solubility; furthermore, the diffusion coefficient (D) values decrease with the increase of their molecular diameter. For HDPE geomembranes served in the landfill liner for 5 years and stretched by 8% of their initial length, KHDPE–W values for organic compounds increase by 5–58%, D values for organic compounds increase by 10–86%, and breakthrough times are faster, indicating more amounts of organic compounds may break through the HDPE geomembrane in fields than expected. The mass transport parameters from MDCA tests could be used with those from batch immersion tests interchangeably after mass loss and immobilization of organic compounds in MDCA tests are considered.     

Diffusive Transport of VOCs through LLDPE and Two Coextruded Geomembranes

The diffusive properties of two coextruded geomembranes, one with a polyamide inner core and the other with an ethylene vinyl-alcohol (EVOH) inner core, and a standard 0.53-mm (20-mil) linear low-density polyethylene (LLDPE) geomembrane were examined. Diffusion and sorption laboratory tests were performed to estimate the parameters controlling diffusive migration, including the partitioning, diffusion, and permeation coefficients of the geomembrane in both the aqueous and vapor phases. Results indicate a significant reduction in mass flux through the coextruded geomembranes compared to conventional LLDPE. The EVOH coextruded geomembrane had the lowest permeation coefficients (Pg) with a range of (2–6)×10?12?m2?s?1 for diffusion from the aqueous phase. These values for EVOH are upper bounds and the actual values may be lower than as stated. The polyamide (nylon) coextruded geomembrane had higher values than for EVOH, with a Pg range of (0.7–2.2)×10?11?m2?s?1 from the aqueous phase. The highest permeation coefficients were for the standard 20-mil LLDPE, which ranged from (0.6–1.1)×10?10?m2?s?1. Thus the permeation coefficient for LLDPE was about one order of magnitude greater than for the nylon coextruded and at least two orders of magnitudes higher than for the EVOH coextruded geomembrane. Both coextruded geomembranes showed decreased Pg values and therefore improved diffusive resistance to volatile organic compounds over traditional 0.56-mm PVC geomembranes. The EVOH geomembrane showed a 5–12-fold decrease in Pg in comparison to a 2.0-mm high density polyethylene geomembrane.     

Relating Batch and Column Diffusion Coefficients for Leachable Contaminants in Particulate Waste Materials

For constructed facilities in which waste materials are used as partial substitutes for traditional aggregates, it is usually necessary to perform contaminant leachability tests to assess the long-term emission of contaminants from the facilities during service. Such tests can be performed under batch and column flow-through conditions. It is usually desirable to establish the relationship between leached contaminant concentrations obtained through both tests. Using Al and Cu diffusion coefficients as the target parameter, an analytical model is developed and presented herein with experimental data from acidic solution (pH of 4.5) leach testing of asphalt concrete that was amended with municipal solid waste incinerator bottom ash in weight percentages ranging from 0 to 20 to assess the equivalence of both sets of leaching conditions. The results for Al show that at higher column flowrates indexed by Peclet numbers in excess of 5.5, there is no defined relationship between Al diffusion coefficients obtained through both methods. Fluid flow at lower Peclet numbers approach batch conditions and afford an opportunity for the use of the analytical model presented in this paper provided comparisons are made at equivalent liquid/solid ratios. The values of the batch diffusion coefficients obtained for Al are of the order of 10?10–10?6?cm2/s. For column leaching of Al, the range is 10?8–10?7?cm2/s. No measurable quantity of Cu was obtained under both batch and column leaching conditions.     

Microscopic Visualization Technique to Predict the Permeation of Organic Solvents through PVC Pipes in Water Distribution Systems

Organic contaminants may permeate through plastic pipes in water distribution systems and adversely affect the quality of drinking water. In this study, we developed a microscopic visualization technique to investigate the permeation of common organic contaminants (benzene, toluene, ethylbenzene, xylene, and trichloroethene) through polyvinyl chloride (PVC) pipes. By observing the propagation of organic moving fronts in the pipe materials with a light microscope, the technique was able to predict the permeation breakthrough times through PVC pipes that were determined in the pipe-bottle test. The advance of an organic moving front was found to be linearly dependent on the square-root of time and the propagation rate increased with an increase in the external organic chemical activity. Permeation of organic mixtures into PVC pipes was found to be additive in proportion to the permeation rates and volume percents of each component. In combination with a 2-year pipe-bottle test for PVC pipes exposed to premium gasoline, mathematical extrapolations based on the microscopic visualization tests predicted that PVC pipe are likely to resist permeation by commercial gasoline for the service life of the pipe.     

Analytical Solution for Diffusion of VOCs through Composite Landfill Liners

Analytical solutions are presented for analyzing volatile organic compound (VOC) diffusion through intact composite landfill liners for two scenarios with boundary conditions at the base of either a VOC concentration of zero or a VOC mass flux of zero. A time-dependent concentration top boundary condition is included in the presented analytical solutions to model typical variations of VOC concentration in the leachate over time. The presented solutions are verified against alternative numerical solutions and applied to analyze dichloromethane diffusion through a composite liner. The analytical solutions are found to provide useful predictions of VOC concentration and mass flux for the design of composite liners. VOC concentrations and fluxes at the base of the composite liner at 30?years predicted by consideration of representative transient variation in leachate concentration, for an example problem, are nearly half of those when a constant leachate concentration assumed.     

Estimation of Polyethylene Oxide Polymer Train and Loop Densities on Contaminant Barrier Materials

Desiccation of exposed clayey materials in cover layers of waste containment systems can ultimately result in the development of cracks that can promote the infiltration of rainwater and/or snowmelt, and escape of gases from buried wastes. Clayey barriers can be stabilized against desiccation by introducing binders such as concentrated polymer liquids or aqueous solutions. In this research, a theoretical analysis of the morphological configuration of molecules of polyethylene oxide (PEO) on montmorillonite (a common barrier mineral) was performed. A methodology for estimating polymer train and loop densities using batch sorption measurements was developed and demonstrated using PEO sorption test data for sodium montmorillonite (specific surface area: 31.82±0.22 m2/g) at initial aqueous PEO (molecular weight 8,000,000) concentrations of 0, 0.5, 1.0, 2.0, and 4.0 g/L. From test data, the distribution coefficient of PEO was determined to be 0.1599 mL/g. The analyses indicate that the distribution of sorbed PEO molecules into trains and loops is very sensitive to PEO chain flexibility. For example, for a function of partition function (λ) value of 0.1, the numbers of PEO molecular trains on 1 g of sodium montmorillonite are estimated to be 3.4×1020 and 4.7×1020 for chain flexibilities of 0.2 and 0.8, respectively. The greater the chain flexibility, the greater the opportunity for polymer molecules to lie flat on clay particles. Within an initial PEO concentration range of 0–4.0 g/L, no significant dependence of sorbed polymer molecular configuration on initial concentration was found. Possibly, extension of sorbed polymer molecular loops into barrier soil pores narrows fluid flow channels and hence the desiccation rate. This research enhances understanding of the physico-chemical processes that underlie clay stabilization by aqueous polymers.     

Characterizing Polyurethane Foam as a Sink for or Source of Volatile Organic Compounds in Indoor Air

Polyurethane foam (PUF) is widely used in indoor consumer products. Despite strong potential interactions with volatile organic compounds (VOCs), the effect of PUF on indoor concentrations of VOCs has not been examined. This study determines the behavior of PUF as a potential sink for or source of VOCs in indoor air. A flexible polyether-type foam and eight aromatic VOCs ranging in molecular weight from naphthalene to benzene were studied. Rapid determinations of PUF–air partition coefficient (K) and PUF–phase diffusion coefficient (D) were achieved using a dynamic microbalance procedure. A diffusion model was applied to interpret the experimental data. The PUF sample was assumed to conform to semi-infinite cylindrical geometry with solid-phase diffusion being the rate limiting step. The results indicate that sorption of VOCs by PUF is fully reversible. For the VOCs studied, K can be correlated with vapor pressure and D with molecular free surface area. Humidity appears to reduce the extent of sorption and slow the sorption kinetics. These findings should facilitate the prediction of the source/sink behavior of PUF and the related impact on VOC concentrations in the indoor environment.