| Summary: | Thesis (Ph.D, Civil Engineering) -- Queen's University, 2010-05-01 08:12:38.382 The diffusive transport of volatile organic compounds (VOCs) through geomembranes is examined. The key diffusive parameters: diffusion (Dg), partitioning (Sgf) and permeation (Pg) coefficients, for transport from both vapour and aqueous phases are evaluated. Consideration is given to different types of geomembrane, exposure to cold climatic conditions, and aged geomembranes exhumed after 3 and 25 years. Laboratory sorption and diffusion tests are performed and modeling is used to infer diffusive parameters from experimental data. The transport of VOCs through polyvinyl chloride (PVC) and linear low-density polyethylene (LLDPE) geomembranes from both aqueous and vapour phases is evaluated by Purge & Trap-GC/MS. Results indicate that VOC transport through geomembranes in a simulated landfill environment is identical despite the phase they originate from. Subsequently, this finding is confirmed by examining diffusion of vapour-phase VOCs using Solid Phase Microextraction-GC/FID. Diffusive transport of VOCs through traditional PVC, LLDPE and high-density polyethylene (HDPE) geomembranes is compared with that through two novel co-extruded geomembranes, one with a polyamide inner core, the other an ethylene vinyl alcohol (EVOH) inner core. Both co-extruded geomembranes show a 10-200-fold decrease in Pg values and therefore improved diffusive resistance to VOCs compared to the traditional geomembranes. EVOH also shows a 5-12-fold decrease in Pg values compared to an HDPE geomembrane. The effects of cold environments on the diffusion of VOCs are studied. Five geomembranes are exposed to simulated cold climatic conditions in the laboratory. Results from diffusion tests run at 2-24oC indicate Dg and Pg decrease with temperature. The temperature and diffusion coefficients relationship follow the Arrhenius equation. Activation energies of diffusion are calculated specific to each geomembrane and contaminant. An HPDE geomembrane taken from a field site in the Canadian Arctic after three years of exposure to cold climatic conditions shows minimal decreases in Dg and Pg when compared to new HDPE. Finally, the diffusion of VOCs through an HDPE geomembrane exhumed from a decommissioned PCB landfill originally built in 1984 is examined. Profiling of PCB concentrations in the landfill clay and composite liners is investigated indicating minimal PCB diffusive migration after 25 years. PhD
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