Model Non-aqueous Phase Liquids Research Articles

An experimental study of in-situ remediation of NAPL-polluted soils by ozonation

The effectiveness of ozonation as a method for the in situ remediation of non-aqueous phase liquid (NAPL)-polluted soils is examined. Soils were polluted artificially with a model NAPL consisting of equal mass fractions of n-decane, n-dodecane and n-hexadecane at two concentrations 1g/kg-soil, and 10g/kg-soil. The polluted soils were placed inside a stainless steel column and treated with the injection of ozone-rich gas, produced from oxygen by a corona discharge ozone generator, controlled by a gas mass flow controller, and monitored by an ozone analyzer. Soil samples collected from the soil column were used after pre-treatment to measure the concentrations of the total organic carbon (TOC), and total petroleum hydrocarbons (TPH) as function of time. The concentrations of carbon dioxide (CO2), carbon monoxide (CO), nitrogen oxides (NOx), and volatile organic compounds (VOCs) were detected on-line by a multi-sensor and portable gas analyzer. .

Chemotaxis Increases the Retention of Bacteria in Porous Media with Residual NAPL Entrapment.

Chemotaxis has the potential to decrease the persistence of nonaqueous phase liquid (NAPL) contaminants in aquifers by allowing pollutant-degrading bacteria to move toward sources of contamination and thus influence dissolution. This experimental study investigated the migratory response of chemotactic bacteria to a distribution of residual NAPL ganglia entrapped within a laboratory-scale sand column under continuous-flow at a superficial velocity of 0.05 cm/min. Naphthalene dissolved in a model NAPL 2,2,4,4,6,8,8-heptamethylnonane partitioned into the aqueous phase to create localized chemoattractant gradients throughout the column. A pulse mixture of equal concentrations of Pseudomonas putida G7, a strain chemotactic to naphthalene, and Pseudomonas putida G7 Y1, a nonchemotactic mutant, was introduced to the column and effluent bacterial concentrations were measured with time. Breakthrough curves (BTCs) for the two strains were noticeably different upon visual inspection. Differences in BTCs (compared to nonchemotactic controls) were quantified in terms of percent recovery and were statistically significant ( p < 0.01). Chemotaxis reduced percent recovery in the effluent by 45% thereby increasing the population of bacteria that were retained within the column in the vicinity of residual NAPL contaminants. An increase in flow rate to a superficial velocity of 0.25 cm/min did not diminish cell retention associated with the chemotactic effect.

Dielectric barrier discharge plasma used as a means for the remediation of soils contaminated by non-aqueous phase liquids

A plane-to-grid dielectric barrier discharge (DBD) reactor operating with air at atmospheric pressure was used to investigate the removal of non-aqueous phase liquids (NAPLs) from soil layers. A mixture of n-C10, n-C12 and n-C16 was used as a model NAPL that polluted the soil at a very high initial concentration (100,000mg/kg-soil). The effect of treatment time, energy consumption, and soil thickness on the NAPL removal efficiency was investigated, the plasma active species were identified, and the macroscopic gas temperature was determined. The NAPL remediation efficiency found to be as high as 99.9% after 60–120s of plasma treatment, depending on soil thickness. The energy density required to remediate completely the NAPL was about 600J/g-soil and was practically independent of the soil thickness, indicating that the DBD-based plasma has the potential to become a highly cost-effective technology for the remediation of NAPL-contaminated soils. N2+, N2∗, NOx and O3 were identified as plasma-induced reactive species, a maximum gas temperature close to 300°C was recorded, and the total carbon detected in exhaust gases, in the form of CO and CO2, was ca 40% of that contained in the NAPL removed from the soil. The main mechanisms of NAPL removal by plasma found to be the evaporation of organic compounds coupled with their oxidation in liquid and gas phase. Using ATR-FTIR in combination with high-throughput organic profiling analysis by GC–MS, ketones and alcohols were identified as the main intermediate products of alkanes oxidation in soil matrix.

Non-aqueous phase liquid-contaminated soil remediation by ex situ dielectric barrier discharge plasma

Non-thermal dielectric barrier discharge plasma is examined as a method for the ex situ remediation of non-aqueous phase liquid (NAPL)-contaminated soils. A mixture of equal mass concentrations (w/w) of n-decane, n-dodecane and n-hexadecane was used as model NAPL. Two soil types differing with respect to the degree of micro-heterogeneity were artificially polluted by NAPL: a homogeneous silicate sand and a moderately heterogeneous loamy sand. The effect of soil heterogeneity, NAPL concentration and energy density on soil remediation efficiency was investigated by treating NAPL-polluted samples for various treatment times and three NAPL concentrations. The concentration and composition of the residual NAPL in soil were determined with NAPL extraction in dichloromethane and GC-FID analysis, while new oxidized products were identified with attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The experimental results indicated that the overall NAPL removal efficiency increases rapidly in early times reaching a plateau at late times, where NAPL is removed almost completely. The overall NAPL removal efficiency decreases with its concentration increasing and soil heterogeneity strengthening. The removal efficiency of each NAPL compound is inversely proportional to the number of carbon atoms and consistent with alkane volatility. A potential NAPL degradation mechanism is suggested by accounting for intermediates and final products as quantified by GC-FID and identified by ATR-FTIR.

Ex Situ Soil Remediation by Cold Atmospheric Plasma Discharge

The goal of the present work is to examine the efficiency of cold dielectric barrier discharge (DBD) plasma as a method for the remediation of soils contaminated by non-aqueous phase liquids (NAPLs) by using an experimental setup that can easily be up-scaled to industrial scale and a model NAPL (mixture of n-C10, n-C12 and n-C16). The effect of several parameters such as soil heterogeneity, NAPL concentration and treatment time on soil remediation efficiency was investigated by treating NAPL-contaminated samples of a homogeneous commercial silicate sand and a moderately heterogeneous loamy sandy soil with ex situ DBD plasma at atmospheric pressure. The energy density varied from 675 to 10125J/g-soil for three NAPL concentrations (1g/kg-soil, 10g/kg-soil, 100g/kg-soil). The concentration and composition of the residual NAPL in soil were determined with extraction in dichloromethane (DCM) and GC-FID analysis. The experimental results revealed that: (i) the NAPL removal efficiency increases rapidly in early times reaching a plateau at late times, where NAPL is removed almost completely (97 to 99.7%); (ii) the soil heterogeneity decreases the rate of NAPL removal efficiency, especially at lower NAPL concentrations; (iii) the rate of NAPL removal efficiency decreases with its concentration increasing.

Surfactant aided biodegradation of NAPLs by Burkholderia multivorans: Comparison between Triton X-100 and rhamnolipid JBR-515

Both chemical surfactants and biosurfactants have been effectively used for the degradation of petroleum hydrocarbons. Chemical surfactants are known to enhance biodegradation effectively while activity of biosurfactants is also comparable and they have the additional advantage of being biodegradable. However, the mode of action of chemical surfactants and biosurfactants may vary. This work was conducted to determine the mode of action of Triton X-100 and rhamnolipid JBR-515 by exploring the factors affecting the process of surfactant aided biodegradation of model non aqueous phase liquids (NAPLs) by a naphthalene degrader, Burkholderia multivorans (NG1). Emulsification studies, growth rate and degradation rate studies were conducted and correlated with alteration in cell surface properties including surface hydrophobicity, cell surface charge and cell surface functional groups. Triton X-100 and JBR-515 demonstrated distinct mode of uptake of NAPLs. Triton X-100 enhanced bioavailability by emulsification and supported direct interfacial uptake of model NAPLs by B. multivorans (NG1). Conversely, the biosurfactant rhamnolipid JBR-515 did not demonstrate emulsification of NAPLs and enhanced bioavailability through micellar solubilization. NAPL composition influenced the alteration in the cell surface properties. For both the surfactants, increase in surfactant concentration increased the rate of utilization of aliphatic hydrocarbons from the NAPLs.

Contaminant Mass Transfer from NAPLs to Water Studied in a Continuously Stirred Flow-Through Reactor

AbstractThe release of nonaqueous-phase liquids (NAPLs) from porous media to groundwater is a widespread environmental problem. The mass transfer of individual NAPL components controls both the extent of groundwater contamination and the persistence of the residual NAPL phase. In order to quantify this key process, small-scale experimental studies on NAPL-water mass transfer were performed in a dynamic system mimicking environmental conditions with “clean” water continuously flowing through the NAPL pool. To describe this process, a modified simulation method was developed and validated by the experimental data. The experimental system consisted of a custom-designed flow cell (with NAPL and water) connected to the peripheral equipment (e.g., pump, water source). This continuously stirred flow-through reactor was used to perform mass transfer experiments with simple and complex model NAPL–water systems. To simulate the experimental data (concentration versus time profiles of individual NAPL compounds), an ...

Treatment of aqueous effluents containing non-aqueous phase liquids in rotating biological contactor with algal bacterial biofilm

Rotating biological contactors (RBCs) have been widely used for treatment of effluents containing soluble organic compounds. This study reports treatment of aqueous effluent containing diesel oil (0.6%) as a model non-aqueous phase liquid (NAPL) in a RBC. The NAPL serves as the sole substrate for the bacterial culture, Burkholderia cepacia that is inoculated along with a sessile algal culture for biofilm formation. After biofilm formation in batch mode, the 3-stage reactor was operated in a flow through mode. Data was collected over the unsteady state and also for steady state operation over hydraulic retention time (HRT) range 12–24h and total petroleum hydrocarbon (TPH) loading range 23.9–47.8gTPH/m2d. Greater than 99% removal could be achieved for TPH loading up to 31.8gTPH/m2d. The models available for predicting removal efficiency of soluble substrate at various HRT values could not be applied for this system. While the assumption of uniform distribution in each stage of the RBC is valid for soluble substrate, it is invalid for NAPLs as illustrated by the unsteady state profile. The stage-wise effluent TPH profiles obtained during unsteady-state operation was indicative of a plug flow reactor with dispersion (PFDR) with sorption and biodegradation occurring simultaneously. The diesel oil in the aqueous phase sorbed on the algal–bacterial biomass and bulk of the aliphatic fraction was biodegraded. The aromatic fraction of diesel accumulated on the biofilm. This system is very complex and new models need to be formulated for understanding and elucidating treatment of NAPL containing aqueous effluents in RBCs.

Alteration in cell surface properties of Burkholderia spp. during surfactant-aided biodegradation of petroleum hydrocarbons

Chemical surfactants may impact microbial cell surface properties, i.e., cell surface hydrophobicity (CSH) and cell surface charge, and may thus affect the uptake of components from non-aqueous phase liquids (NAPLs). This work explored the impact of Triton X-100, Igepal CA 630, and Tween 80 (at twice the critical micelle concentration, CMC) on the cell surface characteristics of Burkholderia cultures, Burkholderia cepacia (ES1, aliphatic degrader) and Burkholderia multivorans (NG1, aromatic degrader), when grown on a six-component model NAPL. In the presence of Triton X-100, NAPL biodegradation was enhanced from 21% to 60% in B. cepacia and from 18% to 53% in B. multivorans. CSH based on water contact angle (50-52°) was in the same range for both strains while zeta potential at neutral pH was -38 and -31 mV for B. cepacia and B. multivorans, respectively. In the presence of Triton X-100, their CSH increased to greater than 75° and the zeta potential decreased. This induced a change in the mode of uptake and initiated aliphatic hydrocarbon degradation by B. multivorans and increased the rate of aliphatic hydrocarbon degradation in B. cepacia. Igepal CA 630 and Tween 80 also altered the cell surface properties. For B. cepacia grown in the presence of Triton X-100 at two and five times its CMC, CSH increased significantly in the log growth phase. Growth in the presence of the chemical surfactants also affected the abundance of chemical functional groups on the cell surface. Cell surface changes had maximum impact on NAPL degradation in the presence of emulsifying surfactants, Triton X-100 and Igepal CA630.

Experimental investigation of nonequilibrium capillarity effects: Fluid viscosity effects

Numerical models have been widely used to simulate multiphase flow in porous media for a variety of applications (e.g., NAPL migration in subsurface aquifers, carbon sequestration, agriculture, paper production, and petroleum reservoir development). The relationship between the difference in phase pressures and saturation is used as one of the important constitutive relationships in numerical models. Theoretical studies have suggested that this relationship should include a damping coefficient or capillarity coefficient () on the basis of thermodynamic considerations. A literature review suggests that the magnitude of this capillarity coefficient varies by over three orders of magnitude. While recent experimental studies have explored the effect of porous medium properties, effect of domain size, hysteresis, and the imposed boundary conditions on the magnitude of , there has been no experimental study investigating the impact of fluid viscosity on . This study reports on a series of primary drainage experiments conducted under both static and dynamic conditions in F70 silica sand. Fluid pairs used included water and silicone oil with two differing viscosities and slightly different densities (used as model nonaqueous phase liquids) in addition to air. Water saturation and both wetting and nonwetting phase pressures were measured in a custom‐built aluminum column using EC‐5 probes and tensiometers at three levels. Results show a strong dependence of the magnitude of the capillarity coefficient on effective fluid viscosity. This implies that consideration should be given for the inclusion of a capillarity coefficient in modeling tools used to simulate multiphase flow when fluids saturations are changing rapidly and when fluids have a large viscosity ratio.

Surface hydrophobicity of petroleum hydrocarbon degrading Burkholderia strains and their interactions with NAPLs and surfaces

Bacterial cell surface hydrophobicity (CSH) is an important factor governing the growth and adhesion behavior of microorganisms on non-aqueous phase liquids (NAPLs). In this work CSH and surface charge was quantified for three oil degrading Burkholderia cultures: aliphatic degrader Burkholderia cepacia (ES1) and two strains of aromatic degrading Burkholderia multivorans (NG1 and HN1) based on contact angle and zeta potential measurement. Model non-aqueous phase liquids (NAPLs) were formulated using n-hexadecane, naphthalene, phenanthrene and pyrene in varying concentration. Adhesion on to glass surfaces of varying hydrophobicity and adherence to n-hexadecane was quantified and correlated with hydrophobicity of the surface; variation in CSH of the culture in response to model NAPL used as growth substrate; and variation in zeta potential as a result of variation in growth substrate, ionic strength and pH of resuspension solution. B. cepacia (ES1) and B. multivorans (HN1) depicted comparable CSH which was higher than that of B. multivorans (NG1). For each culture, CSH was found to vary with the model NAPL used as growth substrate. Adhesion to glass increased with increase in CSH of the bacterial culture and with increase in hydrophobicity of the glass surface. B. cepacia (ES1) with lower negative zeta potential consistently depicted greater adhesion compared to B. multivorans (HN1). Adherence to n-hexadecane was significantly affected by various other factors, such as, growth substrate, pH, resuspension solution and their interactions as revealed through statistical analysis. These factors affected both the zeta potential and adherence to n-hexadecane to varying degree for the three Burkholderia cultures.

Effects of growth conditions and NAPL presence on transport of Pseudomonas saccharophilia P15 through porous media

Extensive research has been done to characterize transport of bacteria in porous media; however, little is understood on how the presence of non-aqueous phase liquids (NAPLs) coupled with the growth state and carbon source of bacteria affect bacterial transport. The objective of this research is to quantify the bacterial adhesion of Pseudomonas saccharophilia P15 (P15), which is known to biodegrade polycyclic aromatic hydrocarbons (PAH) and to interact with coal tars, within a NAPL–water–mineral system. Through a series of short-pulse column experiments, the transport and deposition of P15 in porous media (quartz sand) as a function of growth state and carbon sources (peptone and naphthalene), and in the presence and absence of residual NAPL (hexadecane), is measured and evaluated. Coating 20% of the quartz grain with hexadecane as a model NAPL increased the retention of P15 by as much as a factor of 26 as compared to the retention exhibited in quartz sand with no NAPL present. P15 grown on peptone and in the late exponential growth state exhibited a greater amount of deposition within the hexadecane column than when it was grown on naphthalene or was in early exponential growth phase. During early growth stage P15 grown on naphthalene adhered stronger to the porous media compared to when grown on peptone. Results were compared with results of MATH assays, where P15 partitioning to hexadecane was evaluated as a function of carbon source and growth state.

Enhanced Dissolution of Trichloroethene: Effect of Carbohydrate Addition and Fermentation Processes

Remediation of source areas is challenging because lingering contaminants are often present as nonaqueous phase liquid (NAPL) and sorbed mass, and therefore difficult to remove via biodegradation or other commonly used remedial methods. Experimental results indicate that enhanced dissolution of a model NAPL, trichloroethene (TCE), can occur through the addition and/or subsequent fermentation of a dilute molasses solution. Enhanced mass transfer occurs by two mechanisms, depending upon whether the molasses solution is fresh or has fermented. The addition of fresh molasses worked to increase TCE solubility (>200%), thereby increasing mass transfer from the NAPL phase. Mixing TCE NAPL with a fermented molasses solution, however, increased TCE mass flux via the formation of a NAPL/aqueous phase emulsion. In addition, fermented liquid may have also decreased the soil partitioning coefficient (Kd) of TCE, indicating that enhanced transfer of sorbed mass to the aqueous phase could also occur in the presence of fermented molasses. These results provide guidance on how remedial systems may be optimized to increase NAPL and sorbed-mass dissolution and are therefore important, particularly when bioremediation is used to polish residual source zones.

Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM

Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin. Headspace SPME was used for analyzing PAH since the presence of a complex or dirty matrix in direct contact with the fiber may damage it. Four model PAHs-anthracene, fluorene, phenanthrene, and pyrene-were analyzed by GC-MS. Negligible depletion SPME technique was used to determine the free fraction. Total PAH was determined by enhancing the mass transfer from the bonded phase to the freely dissolved phase by temperature optimization and the use of the method of standard additions. The PAH absorption kinetics were determined in order to define the optimal sampling conditions for this method. The fitting of the experimental data to a mathematical model was accomplished using Berkeley Madonna software. Humic acid and silicon oil were used as model NOM and NAPL, respectively, to study the effect of these compounds on the decrease of SPME response. Then, the method was evaluated with wastewater from a fuel station spill retention basin. The SPME kinetic parameters-k (1) (uptake rate), k (2) (desorption rate), and K (SPME) (partition coefficient)-were determined from experimental data modeling. The determination of the free fraction required 15-min sampling to ensure that PAH depletion from sample was below 1%. For total PAH, a 30-min extraction at 100 degrees C ensured the maximum signal response in the GC-MS. For the determination of free and total PAHs, extractions were performed before reaching the SPME equilibrium. The wastewater used in this study had no free fraction of the analyzed PAHs. However, the four studied PAHs were found when the method for total PAH was used. The addition of NOM and NAPL dramatically decreased the efficiency of the SPME. This decrease was the result of a greater partition of the PAHs to the NAPL and NOM phases. This fact was also observed in the analysis of the fuel station spill retention basin, where no free PAH was measured. However, using the method of standard addition for the determination of total PAH, it was possible to quantify all four PAHs. The method developed in the present study was found to be adequate to differentiate between free and total PAH present in oily wastewater. It was determined that the presence of NOM and NAPL had a negative effect on SPME efficiency. The presence of binding substances had a great influence on SPME kinetics. Therefore, it is of extreme importance to determine their degree of interference when analyzing oily wastewaters or results can otherwise be erroneous. Other factors influencing the total PAH determinations should be considered in further studies.

Mass transfer and bioremediation of aromatics from NAPL in a baffled roller bioreactor

A non-aqueous phase liquid (NAPL) containing dissolved naphthalene or phenol was used to simulate water insoluble contaminants which are produced during the processing of oil sands. Mass transfer and biodegradation of organic contaminants in the aqueous phase were studied in a baffled roller bioreactor. Mass transfer of both naphthalene and phenol from NAPL into the aqueous phase was completed in less than 60 min, by which time naphthalene reached its saturation concentration in the aqueous phase and phenol was completely transferred into the aqueous phase. Pseudomonas putida (ATCC 17484) was subsequently used in biodegradation experiments in the baffled bioreactor containing the model NAPL contaminant. The optimum loading of NAPL for biodegradation of naphthalene at 500 mg/L was found to be 40%. High biodegradation rates (136.4 mg/L h for naphthalene and 13.2 mg/L h for phenol based on the working volume of the bioreactor) were achieved. In the case of simultaneous biodegradation of naphthalene and phenol, the highest total biodegradation rate of 102.6 mg/L h was achieved.

MRI studies of flow and dislocation of model NAPL in saturated and unsaturated sediments

SummaryIn this article, we explore the possibilities of studying transport phenomena that involve non‐aqueous phase liquids (NAPL) by means of magnetic resonance imaging (MRI) with a paramagnetic contrast agent. We studiedn‐octanol as a model NAPL, especially in alcohol flooding in a water‐saturated sediment, and flood‐drainage‐cycles in a temporally unsaturated sediment column. While the ‘natural’ relaxation time contrast between water andn‐octanol often allows a distinction of the two liquids in a quartz‐sand sediment, the use of Mn2+‐ions dissolved in the water phase as a ‘biphasic’ contrast agent allows much better discrimination between the different liquid phases and also considerably faster imaging. Using a 3D FLASH sequence, a NAPL‐saturated region can be visualized against a background of water‐saturated sediment in 11 s with a resolution of 1.9 × 1.9 × 3.2 mm3.

Influence of a nonaqueous phase liquid (NAPL) on biodegradation of phenanthrene

A series of batch reactor experiments was carried out to examine the effect of a nonaqueous phase liquid (NAPL) on the biodegradation of a hydrophobic solute. A mathematical program model that describes physical processes of solute solubilization and partitioning between the NAPL and aqueous phases as well as microbial degradation and oxygen utilization was used to analyze the test data. The model calculates the cumulative changes in concentration of substrate, cell mass, carbon dioxide, and dissolved oxygen as a function of time. The equations incorporate the effects of solute solubilization, partitioning, biodegradation, as well as oxygen availability. Hexadecane was used as the model NAPL and was not biodegraded in the timeframe of the experiments performed. The model solute was the polyaromatic hydrocarbon, phenanthrene. In agreement with several previous studies, experimental measurements showed that hexadecane increased rates of mineralization of 15 mg phenanthrene when present at low mass but decreased rates at high mass. Model results suggest that partitioning of the phenanthrene into the hexadecane phase limits bioavailability at high NAPL mass. Further the model suggests that mineralization rates were higher with the low NAPL mass because aqueous phenanthrene concentrations were higher in those treatments from ca. 20 to 40 h than in other treatments. Finally, experiments showed that the presence of hexadecane, at all masses tested, resulted in a lower cell yield, effectively increasing the amount of CO(2) produced during the experiment. Model results suggest that this is due to changes in phenanthrene metabolism that are induced by the presence of the hexadecane phase. Model studies aimed at increasing rates of biodegradation by modifying operating conditions are described along with practical approaches to implementing these modifications.

Reuse of Fly Ash-Amended Petroleum-Contaminated Soils in Highway Embankments

Remediation of contaminated soil and groundwater has been an important task for engineers and scientists in recent years. One of the sources of soil and groundwater contamination in the United States is petroleum spills. A laboratory study evaluated the geotechnical engineering properties and environmental suitability of remediated petroleum-contaminated soils for their possible use in highway construction. The laboratory test program included compaction, batch sorption, and long-term column leaching tests. Diesel fuel, naphthalene, and a model nonaqueous phase liquid (NAPL) were used as the pollutants; waste coal fly ash that included high carbon content was used to stabilize the contaminated soils. Compaction test results indicated that the maximum unit weights and optimum liquid contents of the stabilized soils satisfy the limits set for highway embankment construction. The results of the batch-scale adsorption tests conducted on the fly ash revealed that the ash has good naphthalene sorption propertie...

Reuse of Fly Ash–Amended Petroleum-Contaminated Soils in Highway Embankments

Remediation of contaminated soil and groundwater has been an important task for engineers and scientists in recent years. One of the sources of soil and groundwater contamination in the United States is petroleum spills. A laboratory study evaluated the geotechnical engineering properties and environmental suitability of remediated petroleum-contaminated soils for their possible use in highway construction. The laboratory test program included compaction, batch sorption, and long-term column leaching tests. Diesel fuel, naphthalene, and a model nonaqueous phase liquid (NAPL) were used as the pollutants; waste coal fly ash that included high carbon content was used to stabilize the contaminated soils. Compaction test results indicated that the maximum unit weights and optimum liquid contents of the stabilized soils satisfy the limits set for highway embankment construction. The results of the batch-scale adsorption tests conducted on the fly ash revealed that the ash has good naphthalene sorption properties because of the presence of high carbon content in its structure. Column leaching test results suggested that the naphthalene and o-xylene concentrations in the effluents collected from the fly ash–stabilized specimens were lower than those collected from the control specimens (i.e., borrow material). The findings indicate that the high carbon content fly ashes can be good sorptive agents for remediation of petroleum contaminated soils because of their low cost and presence of high carbon content. However, caution should be exercised when the laboratory results are carried to field conditions, because the level of contamination is likely to influence the leaching properties.

Engineered Polymeric Nanoparticles for Bioremediation of Hydrophobic Contaminants

Sorption of hydrophobic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), to soil has been shown to limit their solubilization rate and mobility. In addition, sequestration of contaminants by sorption to soil and by partitioning in nonaqueous phase liquids (NAPLs) reduces their bioavailability. Polymeric nano-network particles have been demonstrated to increase the "effective" solubility of a representative hydrophobic organic contaminant, phenanthrene (PHEN) and to enhance the release of PHEN from contaminated aquifer material. In this study, we investigate the usefulness of nanoparticles made from a poly(ethylene) glycol modified urethane acrylate (PMUA) precursor chain, in enhancing the bioavailability of PHEN. PMUA nanoparticles are shown to increase the mineralization rate of PHEN crystal in water, PHEN sorbed on aquifer material, and PHEN dissolved in a model NAPL (hexadecane) in the presence of aquifer media. These results show that PMUA particles not only enhance the release of sorbed and NAPL-sequestered PHEN but also increase its mineralization rate. The accessibility of contaminants in PMUA particles to bacteria also suggests that particle application may be an effective means to enhance the in-situ biodegradation rate in remediation through natural attenuation of contaminants. In pump-and-treat or soil washing remediation schemes, bioreactors could be used to recycle extracted nanoparticles. The properties of PMUA nanoparticles are shown to be stable in the presence of a heterogeneous active bacterial population, enabling them to be reused after PHEN bound to the particles has been degraded by bacteria.