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.     

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.     

Hydraulic Conductivity of Bentonite Slurry Mixed Sands

The hydraulic conductivity (k) of specimens from columns containing initially dry sands mixed with bentonite slurries was measured. The mixed specimens represented a range in void ratios (0.672 ≤ e ≤ 3.94) and bentonite contents (0.61% ≤ BC ≤ 7.65%, by dry weight). The measured k values, which ranged from 2.4×10?7?cm/s to 6.8×10?4?cm/s, correlated poorly with the total void ratio (e) of the specimens, due to the complicating effect of the bentonite in the sand-bentonite slurry mixtures. However, the measured k values correlated better with the void ratio of the bentonite (eb), which is consistent with the results of previous studies involving permeation of compacted bentonite and sand-bentonite specimens, even though the range in values of eb in this study (42.5 ≤ eb ≤ 127) was much higher than that previously reported. The relatively large range in eb values for the sand-bentonite slurry mixtures was also consistent with the relatively large range in measured k values, which are about one to seven orders of magnitude higher than values of k commonly reported for compacted sand-bentonite mixtures, despite similar bentonite contents. In terms of bentonite content, addition of more than 3% bentonite via slurry injection and mixing with the sands was successful in reducing the k of the unmixed sands (9.4×10?3?cm/s ≤ k ≤ 5.4×10?2?cm/s) by as much as four orders of magnitude to values less than 1.0×10?6?cm/s.     

Results from 18 Years of In Situ Performance Testing of Landfill Cover Systems in Germany

The water balances and the long-term performance of different landfill cover systems have been measured in situ in large-scale lysimeters on the landfill Hamburg-Georgswerder, Germany since 1988. The cover systems including different barrier components for water transport were constructed with state-of-the-art technology and have been excavated at several occasions especially to inspect the structure of the barriers. For the first time, the irreversible impact of crack formation in cohesive soil barriers and geosynthetic clay barriers due to desiccation, shrinkage, ion exchange, and plant root penetration has been observed and quantified in this study. After four years of good performance, these covers began to leak between 90 and 200 mm/year (average precipitation of 860 mm/year). The hydraulic conductivity of the cohesive soil barriers increased from 2×10?10 to 9×10?8?m/s, the daily peaks of the leakage through the geosynthetic clay barriers from initial values around 2×10?11?to?2×10?7?m3/(m2?s). The composite barriers with geomembranes above cohesive soil barriers performed very well, showing no leakage and only very little thermally induced water transport. A capillary barrier also performed well (average annual leakage of 18 mm/year). The data of the past 10 years prove that evapotranspiration can be increased significantly by planting bushes, which also limits the potential leakage through barrier layers.     

Transport of Organic Contaminants in Geomembranes under Stress

The transport properties of aqueous solutions of benzene, dichloromethane, and trichloroethylene through extended polyvinyl chloride and high-density polyethylene geomembranes are investigated. It is found that extension enhances the permeation rates of the penetrants through polyvinyl chloride geomembranes, and the opposite effect is found in the case of high-density polyethylene. This difference in response is attributed to the type of structural change, which occurred as a result of the extension. The diffusivities of a mixture of the three organic solvents through the geomembranes are also determined.     

Feasibility of Using Coal Fly Ash for Mine Waste Containment

This study investigates the feasibility of using coal fly ash and fly ash-bentonite mixtures as a barrier material for mine waste. The hydraulic conductivity of the coal fly ash was measured to be in the order of 2×10?9?m/s when it was permeated with deionized water, and this value decreased significantly when the permeant was switched to acid mine drainage (AMD). The addition of bentonite to coal fly ash lowered the hydraulic conductivity during water permeation but no further significant change was observed upon switching the permeant to AMD. Chemical analyses on the effluent from the hydraulic conductivity tests indicated that heavy metals present in AMD were attenuated and were well below the leachate criteria set by the Ontario Government. X-ray diffraction and scanning electron microscopy analyses results of postpermeation samples showed significant structural differences and formation of secondary minerals after AMD permeation. The results of this study suggest that the addition of 10% bentonite to coal fly ash reduced the hydraulic conductivity of the coal fly ash to less than 1×10?9?m/s and improved the chemical compatibility for mine waste containment.     

Estimation of Diffusion Coefficients and Solubilities for Organic Solvents Permeation through High-Density Polyethylene Geomembrane

Experiments on the permeation of several chlorinated and aromatic hydrocarbons through high-density polyethylene (HDPE) geomembranes were conducted using the ASTM F-739 standard test method. The diffusion coefficients were estimated by a one-dimensional diffusion equation based on Fick’s second law, and the solubilities of the solvents in HDPE were determined by the steady state permeation rates. The one-dimensional transient model was able to simulate the permeation concentrations and implied that equilibrium partition between organic solvent and HDPE geomembrane was not achieved during the initial permeation. The solubilities of organic solvents in the HDPE geomembranes obtained by immersion tests or weight gain methods of permeation experiments were not an appropriate boundary condition for the model simulation of permeation. It was found that the diffusion coefficients and solubilities of organic solvents correlated well with their molecular weights and dipole moment, respectively. The present work provides information on the extent of organic compounds permeations through HDPE geomembranes as applied in hazardous waste landfills.     

Diffusive Transport of Permanganate during In Situ Oxidation

The transport of permanganate in low permeability media (LPM) and its ability to degrade trichloroethylene (TCE) in situ were studied through diffusive transport experiments with intact soil cores. A transport cell was developed to measure the effective diffusion coefficient (Deff) of a Br? tracer through intact cores of silty clay LPM obtained from a field site and enable calculation of the apparent tortuosity (τa) of the medium. Then, 5000 mg?L?1 of KMnO4 was added to the cell and diffusive transport and soil matrix interactions were observed. After three months, the soil cores were dissected for morphologic examination and characterization of matrix ions, total organic carbon, MnO4?, and manganese oxides (MnO2). The experiment was then repeated after 2 μL of pure phase TCE were delivered into the center of each of two intact cores. Permanganate transport was observed for one month and then an extraction of the entire soil core was made to determine the extent of TCE degradation. This research demonstrated that permanganate can migrate by diffusion and yield reactive zones that can be predicted based on the properties of the LPM and the oxidant source. Under the experimental conditions examined, permanganate had little effect on the LPM’s pore structure or continuity, and appreciable soil organic matter remained even after 40–60 days of exposure to the oxidant. MnO2 solids, an oxidation by-product, were observed in the LPM, but not at levels sufficient to cause pore filling or alter the apparent matrix tortuosity, even when TCE was present. During diffusive transport of permanganate, TCE in the silty clay LPM was degraded by 97%.     

Modeling TOC Breakthrough in Granular Activated Carbon Adsorbers

Linear regression techniques were used to develop practical models to predict total organic carbon (TOC) breakthrough in bituminous granular activated carbon (GAC) adsorbers. Models were developed for two field-scale GAC sizes (8×30 and 12×40?mesh) and two empty bed contact times (EBCTs) (10 and 20 min). Model input parameters include two water quality variables, influent TOC concentration (TOC0) and pH, that impact performance. The dependent variables for the models were normalized breakthrough time, throughput in bed volumes, to six fractional (TOC/TOC0 = 0.2, 0.3, 0.4, 0.5, 0.6, and 0.7) and three mass (TOC = 1.0, 1.5, and 2.0 mg/L) effluent concentrations. Model development was performed using small-scale breakthrough data from 35 different source waters; external model validation was performed with small-scale breakthrough data from 14 source waters; a sensitivity analysis was performed to ensure that the models effectively capture expected breakthrough trend; and a scalability test was performed to verify the models’ ability to predict breakthrough for field-scale GAC adsorbers.     

Treatment of TCE-Contaminated Groundwater Using Fenton-Like Oxidation Activated with Basic Oxygen Furnace Slag

The industrial solvent trichloroethylene (TCE) is among the ubiquitous chlorinated organic compounds found in groundwater contamination. The objective of this study was to evaluate the potential of applying basic oxygen furnace (BOF) slag as the catalyst to enhance the Fenton-like oxidation to remediate TCE-contaminated groundwater. Results indicate that TCE oxidation via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/quartz sand media was iron oxyhydroxide (α-Fe2O3). Approximately 81% of TCE removal was observed (with initial TCE concentration of approximately 5?mg?L?1), with the addition of 1,000?mg?L?1 of H2O2 and 10?g?L?1 of BOF slag. Results also show that TCE concentrations dropped from 5 to 1.1?mg?L?1, and chloride concentrations increased from 0 to 2.7?mg?L?1 after 60 min of reaction with the presence of H2O2 and BOF slag. This indicates that the depletion of TCE corresponded with the oxidation reactions and release of chloride ions very well in this study. Results demonstrate that the BOF slag can be used to supply catalysts continuously, and it can be installed in a permeable barrier system to enhance the Fenton-like process in situ.     

Organo-Illite as a Low Permeability Sorbent to Retard Migration of Anionic Contaminants

Landfill leachate, often having high concentrations of metal cations, anions, and organic compounds, presents a great threat to nearby groundwater. Due to negative charges on soil particles, regular clay liners cannot effectively retard the movement of anionic contaminants such as chromate. In this paper, a natural illite was modified by cationic surfactants with different chain lengths and tested for its chromate removal efficiency. When the surfactant tail group is relatively short and the solution critical micelle concentration is high, the sorbed surfactant molecules form a monolayer on illite, resulting no chromate sorption by the organo-illite. As the chain length of surfactant tail group increases, the critical micelle concentration reduces and the surfactant molecules sorb as admicelles on illite with the surfactant sorption exceeding the illite’s cation-exchange capacity. Such admicelle modification makes the organoclay capable of retaining chromate instantaneously and retarding the movement of chromate by 1–2 orders of magnitude. The illite’s hydraulic conductivity showed a slight increase after surfactant modification, from 1×10?7 to 8×10?7?cm/s, probably due to reduced packing density after modification. Chromate breakthrough data from column transport experiments were well described by a one-dimensional advection-dispersion model that incorporated Langmuir sorption.     

Experimental Investigation of Shear Capacity of Precast Reinforced Concrete Box Culverts

This study presents an experimental program to investigate the shear capacity of precast reinforced concrete box culverts. Each culvert was subjected to monotonically increasing load through a 254?mm×508?mm (10?in.×20?in.) load plate in order to simulate the HS20 truckload per AASHTO 2005. Instrumentation included strain gauges, high-resolution laser deflection sensor, and automated data acquisition. Four tests were conducted on 1.22?m×1.22?m×1.22?m (4?ft×4?ft×4?ft) box culverts. The location of the load plate was varied to identify the position, which introduces the maximum shear stresses. Laser sensor data and dial gauge readings were recorded to measure the deflection profile of the box culvert. Strain gauges were placed on the steel reinforcement to measure axial strain at locations of maximum positive and negative bending moments. The test results include reporting the loads at which each crack initiated and propagated. The displacement profile of the top slab from the laser instrumentation output along with the load versus maximum deflection for each culvert is also reported.     

Effects of Seepage Velocity and Temperature on the Dechlorination of Chlorinated Aliphatic Hydrocarbons

The influence of seepage velocity and groundwater temperature on the dechlorination rates of trichloroethylene (TCE) and tetrachloroethylene (PCE) by zero-valent iron (Fe0) were investigated by running laboratory column tests at seepage velocities ranging from 31 to 1,884?m/year at temperatures of 10 and 23°C. By increasing the seepage velocity from 31 to 1,884?m/year at 10°C, there were approximately seven- and nine-fold increases in the normalized dechlorination rate constants (SA) of TCE and PCE, respectively. Similarly, a four-fold increase in the SA of TCE and PCE was also observed at 23°C when increasing the seepage velocity from 103 to 1,183?m/year. Raising the groundwater temperature from 10 to 23°C at a given seepage velocity resulted in 2.7 and 1.1 times increases in the TCE SA and PCE SA, respectively. With the application of the Arrhenius equation, activation energies of 70.3?kJ/mol for TCE and 38.6?kJ/mol for PCE dechlorination were determined, indicating domination of the electron transfer process over the mass transfer as a major rate-limiting step of the dechlorination reactions by Fe0.     

树脂吸附铜锌离子的数值模拟

镀金原料氰化亚金钾的生产过程含氰废液中锌（Ⅱ）离子和铜离子（Ⅱ）浓度较高，为探究树脂吸附铜、锌离子的规律，运用Aspen Adsorption数值模拟软件对Φ10 mm×200 mm的树脂固定床吸附过程进行数值模拟，采用一阶迎风差分法作为偏微分方程的离散方法，研究不同条件下的吸附穿透曲线和吸附负荷分布曲线.结果表明:增加进料流量和进料浓度均可提高吸附效率，传质系数（K_S）大于临界值时，吸附穿透曲线不再受其影响，K_S（Zn2+）=4.3×10-3s-1, K_S（Cu2+）=1.00×10-2s-1.      

Demonstration of efficient trichloroethylene biodegradation in a hollow-fiber membrane bioreactor

Rapid cometabolism of trichloroethylene (TCE) by pure cultures of Methylosinus trichosporium OB3b PP358 was demonstrated in a two-stage hollow-fiber membrane bioreactor over the course of 3 weeks. PP358 was grown in a continuous-flow chemostat and circulated through the shell of a hollow-fiber membrane module (HFMM), while TCE contaminated water (160 to 1450 micrograms/L) was pumped through the fiber lumen (fiber interior). In parallel-flow HFMM biological experiments, 82% to 89% of the influent TCE was removed from the lumen (5.1-min residence time) with 99% of the transferred TCE undergoing biodegradation. Biological experiments in a larger capacity baffled radial-flow HFMM resulted in 66% to 99% TCE transferred and 93% to 96% TCE biodegradation at lumen residence times of between 1.5 and 3.7 min. Biodegradation was maintained throughout the experiments at pseudo-first-order biodegradation rate constants of 0.41 to 2.8 L/mg TSS/day. Best-fit computer modeling of the baffled radial-flow biological process estimated mass transfer coefficients as large as 2.7 x 10(-2) cm/min. The computer model was also shown to simulate the experimental results quite well.     

Foundry Green Sands as Hydraulic Barriers: Laboratory Study

A laboratory testing program was conducted to assess the use of foundry sands from gray iron foundries, typically called green sands, as hydraulic barrier materials. Foundry green sands are mixtures of fine uniform sand, bentonite, and other additives. Specimens of foundry sand were compacted in the laboratory at a variety of water contents and compactive efforts and then permeated in rigid-wall and flexible-wall permeameters to define relationships between hydraulic conductivity, compaction water content, and dry unit weight. Additional tests were conducted to assess how hydraulic conductivity of compacted foundry sand is affected by environmental stresses such as desiccation, freeze-thaw, and chemical permeation. Results of the tests show that the hydraulic conductivity of foundry sand is sensitive to the same variables that affect hydraulic conductivity of compacted clays (i.e., compaction water content, and compactive effort). However, hydraulic conductivities <10?7 cm∕s can be obtained for many foundry sands using a broad range of water contents and compactive efforts, including water contents dry of optimum and at lower compactive effort. The hydraulic conductivity of foundry sand was generally unaffected by freeze-thaw, desiccation, or permeation with 0.1 N salt solution or municipal solid waste leachate, but was incompatible with acetic acid (pH = 3.5). Hydraulic conductivity of foundry sands correlates well with bentonite content and liquid limit, with hydraulic conductivity less than 10?7 cm∕s being achieved for bentonite content ≥6% and∕or liquid limit >20.     

Physical Properties of Vegetable Oil and Chlorinated Ethene Mixtures

Laboratory experiments were conducted to investigate the abiotic interactions of soybean oil (SoyOil) and chlorinated ethene (CE) nonaqueous phase liquids (NAPLs). The mixed NAPL density and interfacial tension behaved ideally, as predicted by the volume ratio. The mixed NAPL viscosity increased exponentially from that of the pure CE to that of pure SoyOil as the volume fraction increased. The measured contact angle was highly variable and was unpredictable as a function of the volume composition of the mixed NAPL. The physical property effects indicate that the mobilization of residual CE NAPLs because of SoyOil injection is unlikely. Equilibrium dissolution of CEs from the NAPL mixtures behaved linearly as a function of the mole fraction. Dissolved SoyOil in simulated groundwater enhanced the dissolution of trichloroethene (TCE) during flow tests, increasing the effluent TCE concentration from 141?to?202?mg/L. The ready intermingling of the CE dense nonaqueous phase liquids (DNAPLs) and SoyOil indicate that such interactions may be significant at sites where vegetable oil is injected into DNAPL source areas to enhance in situ anaerobic bioremediation.     

Experimental Investigation of the Interaction of Soil Air Permeability and Soil Vapor Extraction

Soil vapor extraction column experiments were performed to investigate contaminant removal and its interaction with soil air permeability. Water, TCE, and PCE, and a mixture of TCE and PCE were used as contaminants. Three gradations of Ottawa sand were used at relative densities of 0.60 and 1.0:?medium, fine, and uniform. Soil air permeability was found to increase linearly with time by 25–150?% to a maximum value when the contaminant was completely removed. The largest increase in soil air permeability was found for fine and/or dense samples. The experimental data were used in a previously developed model by Farhan in 1998 and Farhan et al. in 2001 to predict column behavior. In general, the model predictions were in good agreement with the experimental results. They revealed that the assumption of local equilibrium between the pore air and contaminants is valid for a wide range of pore velocities (2.0–9.2 cm/s).