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.     

影响TiO2催化降解有机物废水效率的主要因素

介绍了近年来国内外有机物废水光催化降解的研究现状，及不同催化剂体系对各种有机物的降解效果。通过对以TiO2为主的光催化剂在不同催化剂结构和不同反应因素等条件下降解效果的比较，论述了TiO2光催化剂的优越性、不足和影响机制。并指出了光催化降解有机物废水技术需要进一步解决的问题。     

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.     

Solidification/Stabilization of Hazardous Wastes Containing Metals and Organic Contaminants

The potential of solidification/stabilization (S/S) technology for the safe disposal of hazardous wastes has wide spread recognition. The purpose of this study was to investigate the effectiveness of portland cement-based S/S technology for the safe disposal of hazardous wastes containing toxic metals and organic contaminants. As hazardous wastes, metal enriched mining residue, adsorbable organic halogens (AOX) containing pulp and paper sludge, and polychlorinated biphenyl (PCB) oil-contaminated soil were used. For S/S of waste, portland cement as a binding agent was mixed with wastes at different ratios. For initial waste characterization, contaminant concentrations and some physical waste characteristics such as particle-size distribution, Atterberg limits, specific gravity, and moisture content yielding the maximum compacted dry density were determined. Waste and cement mixtures were cured for 28 days after compacting the desired waste-cement mixtures at their predetermined optimum moisture contents yielding the corresponding maximum dry densities in cylindrical molds having a height of 71 mm and a diameter of 36 mm. At the end of the 28-day cure period, unconfined compressive strength and hydraulic conductivity measurements were conducted on the solidified samples. Subsequently, solidified samples were crushed for fractionation into two different aggregate sizes (between 1–2 and >2 mm) and subjected to the U.S. Environmental Protection Agency Toxicity Characteristic Leaching Procedure (TCLP). The effectiveness of S/S was assessed by comparing the chemical composition of leachates obtained from TCLP tests of untreated and treated, i.e., S/S waste samples, and comparing values of strength and hydraulic conductivity of solidified waste samples with regulatory requirements. For mining waste, effective application of S/S was achieved for most cases. AOX containing sludge yielded acceptable results in terms of strength and hydraulic conductivity but leachate AOX concentrations were above regulatory levels. The effectiveness of S/S for coarse textured-soils contaminated with a PCB oil was not satisfactory, especially at a cement:soil ratio less than 35%.     

Multiple-Porosity Model for the Transport of Reactive Contaminants in Fissured Soils with Nonequilibrium Partitioning

A multiple-porosity model for the transport of reactive contaminants in fissured media with multiple-source, nonequilibrium partitioning is proposed, widening the scope of existing models. The proposed model extends the bicontinuum, dual-porosity concepts by combining five contaminant compartments: (1) mobile water in the fissures; (2) immobile water in the fissures; (3) water diffusing into the soil matrix; (4) sorption in the fissures; and (5) sorption in the soil matrix. Both instantaneous and nonequilibrium sorption are represented in the fissures. Mobile/immobile compartments, fissured soils, and nonequilibrium sorption have been hitherto treated separately or in pairs. Exchange of contaminants occurs between all compartments. Equations for the model are formulated and transformed into the Laplace domain. Solutions for the one-dimensional problem of a leaking storage tank overlying a fissured soil are found. The effects of the inclusion of various contaminant compartments and exchange parameters are analyzed through numerical experiments.     

Modeling Long-Term Transport of Contaminants Resulting from Dissolution of a Coal Tar Pool in Saturated Porous Media

In this study, a three-dimensional mathematical model for simulating the transport of dissolved contaminants originating from an elliptic-shaped coal tar pool in homogeneous saturated porous media is developed. The methodology of the solution is based on a semianalytical approach that assumes the contaminant source input can be represented by the superposition of a series of consecutive short dissolution pulses. The model accounts for possible solidification of polycyclic aromatic hydrocarbon compounds as the coal tar pool dissolves. A circular-shaped synthetic coal tar pool consisting of 22 components is used for model simulation. Simulations show that even after 130 years of dissolution, the coal tar pool remains a potential groundwater pollution threat despite a significant reduction in overall pool volume.     

Predicting Minimum Carbon Usage for PAC Adsorption of Trace Organic Contaminants from Natural Water

Powdered activated carbon (PAC) is an excellent adsorbent for drinking water treatment of many trace organic contaminants. To evaluate and design a PAC adsorption process for a particular application, it is necessary to know the minimum (lowest economical) carbon (adsorbent) usage (MCU) defined thermodynamically. In this work, an explicit relationship is developed for predicting the MCU required for a desirable level of treatment of a target trace organic compound (TC). The adsorption processes considered are PAC slurry contactors idealized either as batch reactors, plug flow reactors, or continuous-flow stirred tank reactors. Comparing with the ones previously available in the literature, this newly developed relationship, as a predictive tool for practical uses as well, is more accurate because it does not need to assume that the MCU required for target TC removal can always reduce the competing background natural organic matter (NOM) to a level much less than the NOM initial/influent concentration. Applications of the relationship developed herein to PAC adsorption of typical trace organic contaminants in natural water are demonstrated with isotherm data from multiple literature sources.     

Effects of Thickness on the Aging of HDPE Geomembranes

The results of an accelerated aging test program to evaluate the effect of thickness on the depletion of antioxidants from high-density polyethylene (HDPE) geomembranes and subsequent degradation of the physical properties are reported. Three commercially available HDPE geomembranes having nominal thicknesses of 1.5, 2.0, and 2.5 mm were examined. The geomembranes were immersed in a synthetic leachate at 85, 70, 55, and 22°C and tested for oxidative induction time, crystallinity, melt index (MI), tensile properties, and stress-crack resistance. The antioxidant depletion rate for the 1.5 mm geomembrane was faster than for the 2.0 and 2.5 mm geomembranes. Antioxidant depletion time was predicted at representative landfill temperatures of 20–60°C using Arrhenius modeling and was found to increase with geomembrane thickness for the three geomembranes examined. Based on the results of crystallinity, MI, and stress-crack resistance, the degradation of the geomembrane was slowest for the thickest geomembrane. These results suggest that a thicker geomembrane may have a longer service life (other things being equal).     

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.     

Contaminants in commercial dapsone

Three contaminants commonly found in commercial dapsone were identified as 2,4'-sulfonylbis(benzeneamine), 4-(phenylsulfonyl)benzeneamine, and 4-(4'-chlorophenylsulfonyl)benzeneamine. The identities were based on the spectral analysis and unambiguous synthesis of each compound. Solvent-free, pure dapsone was prepared by recrystallization from chloroform.     

Measurements of Sediment Erosion and Transport with the Adjustable Shear Stress Erosion and Transport Flume

Soil and sediments play an important role in water management and water quality. Issues such as water turbidity, associated contaminants, reservoir sedimentation, undesirable erosion and scour, and aquatic habitat are all linked to sediment properties and behaviors. In situ analysis is necessary to develop an understanding of the erosion and transport of sediments. Sandia National Laboratories has recently patented the Adjustable Shear Stress Erosion and Transport (ASSET) Flume that quantifies in situ erosion of a sediment core with depth while affording simultaneous examination of transport modes (bedload versus suspended load) of the eroded material. Core erosion rates and ratios of bedload to suspended load transport of quartz sediments were studied with the ASSET Flume. The erosion and transport of a fine-grained natural cohesive sediment were also observed. Experiments using quartz sands revealed that the ratio of suspended load to bedload sediment transport is a function of grain diameter and shear stress at the sediment surface. Data collected from the ASSET Flume were used to formulate a novel empirical relation for predicting the ratio of bedload to suspended load as a function of shear stress and grain diameter for noncohesive sediments.     

Modeling Uncoupled Solute Transport in Natural Organic Matter Size Fractionation by Ultrafiltration

Physicochemical separation of organic macrosolutes and colloidal particles is routinely required during the analysis of natural, waste, and process waters derived from aquatic and terrestrial environmental samples. This study was conducted to demonstrate the utility of a two-parameter nonlinear permeation coefficient model (PCM) in describing the uncoupled transport of solutes in dilute heterogeneous solutions subjected to batch ultrafiltration (UF). The PCM was used in conjunction with natural organic matter (NOM) permeate data for a natural water and six hydrophobic and hydrophilic subfractions to determine permeation coefficients p and NOM concentrations Cr0 with apparent molecular weight less than membrane specific cutoff values of moderately hydrophilic YC/YM series Amicon? UF membranes. Experimentally measured permeation coefficients p determined for the whole water were found to correlate well with composite permeation coefficients p? calculated using a mass-fraction weighted average of individual NOM subfraction permeation coefficient values. Correlation of experimentally measured and calculated permeation coefficient values (p and p?) indicated that the PCM can adequately describe uncoupled transport of chemically distinct solute fractions during batch UF of heterogeneous dilute solutions.     

Volatile Organic Compound (VOC) Transport through Compacted Clay

Movement of volatile organic compounds (VOCs) through compacted clay liners was investigated using laboratory-scale column and tank tests. Hydraulic conductivity of the compacted clay was not significantly impacted by the introduction of VOCs in concentrations up to 20 mg∕L. Soil-water partition coefficients of the seven VOCs tested had a strong logarithmic relationship with the octanol-water partition coefficient. Partition coefficients from batch tests were in good agreement with those measured directly on soil samples at the termination of the column∕tank tests. The VOCs were degraded in the clay, with estimated half-lives ranging from 2 to 116 days. Mechanical dispersion was not significant in the range of the hydraulic conductivities of the test specimens (i.e., <10?7 cm∕s). Effective molecular diffusion coefficients were mostly in 10?6 cm2∕s and generally decreased with increasing aqueous solubility. Mass transport parameters of VOCs in clay liners can be estimated from laboratory batch tests and properly prepared small-scale column tests. However, accounting for degradation of VOCs and minimizing the number of transport parameters that are simultaneously estimated from a single response-time record are important considerations for accurate determination of transport parameters.     

Predicting Boundary Shear Stress and Sediment Transport over Bed Forms

To estimate bed-load sediment transport rates in flows over bed forms such as ripples and dunes, spatially averaged velocity profiles are frequently used to predict mean boundary shear stress. However, such averaging obscures the complex, nonlinear interaction of wake decay, boundary-layer development, and topographically induced acceleration downstream of flow separation and often leads to inaccurate estimates of boundary stress, particularly skin friction, which is critically important in predicting bed-load transport rates. This paper presents an alternative methodology for predicting skin friction over 2D bed forms. The approach is based on combining the equations describing the mechanics of the internal boundary layer with semiempirical structure functions to predict the velocity at the crest of a bedform, where the flow is most similar to a uniform boundary layer. Significantly, the methodology is directed toward making specific predictions only at the bed-form crest, and as a result it avoids the difficulty and questionable validity of spatial averaging. The model provides an accurate estimate of the skin friction at the crest where transport rates are highest. Simple geometric constraints can be used to derive the mean transport rates as long as bed load is dominant.     

Transport of Colloids and Associated Hydrophobic Organic Chemicals through a Natural Media Filter

In this project, the ability of natural media filtration (NMF) to remove colloidal particles and associated hydrophobic organic compounds from the aqueous phase was evaluated by performing sorption and transport experiments with leaf compost media. Phenanthrene sorption isotherm experiments for compost and model colloidal (latex) particles found that phenanthrene has a greater affinity for the colloidal particles than for the compost materials. In column experiments, the transport of phenanthrene through the NMF in the presence and absence of two colloidal particles with different hydrophobicities [sulfate (more hydrophobic) and carboxylate (less hydrophobic)] showed that the effluent phenanthrene concentration in the presence of colloids, particularly sulfate latex particles, is much higher than that in the absence of colloids. The results from a mathematical model used to evaluate data from the column experiments suggest that enhancement of contaminant transport can be significant under the following conditions: high colloidal concentrations, high partition coefficient between contaminant and colloids, or a slow desorption rate of contaminant from colloids.     

Chloride Ion Transport in Bridge Deck Concrete under Different Curing Durations

During freezing temperatures, ice accumulates on exposed concrete slabs such as bridge decks. Deicing salts such as calcium chloride are applied to control this ice formation. These salts migrate down to the reinforcing steel, and they can break down the passivation layer on steel, causing it to corrode. This paper is part of a broader research study to explore the possibility of opening the bridge decks earlier than the 10–12 days as practiced now, by decreasing the number of wet-mat curing days. Seven concrete mixtures typically used in Texas bridge decks were evaluated for chloride permeability using the ponding test (AASHTO T259). The primary experimental variables were the curing duration, type and percentage of supplemental cementitious materials, type of coarse aggregate, duration of ponding, and the surface preparation of ponded concrete specimens. Results of the investigation indicated that curing duration may be decreased for some concrete mixtures as no apparent improvement was shown after a specific curing duration, which ranged from 2 to 8 days depending on the mix.