Multicomponent Nonaqueous Phase Liquid Research Articles

Effects of mono- and multicomponent nonaqueous-phase liquid on the migration and retention of pollutant-degrading bacteria in porous media

The successful implementation of in-situ bioremediation of nonaqueous-phase liquid (NAPL) contamination in soil-groundwater systems is greatly influenced by the migration performance of NAPL-degrading bacteria. However, the impact and mechanisms of NAPL on the migration/retention of pollutant-degrading bacteria remain unclear. This study investigated the migration/retention performance of A. lwoffii U1091, a strain capable of degrading diesel while producing surfactants, in porous media without and with the presence of mono- and multicomponent NAPL (n-dodecane and diesel) under environmentally relevant conditions. The results showed that under all examined conditions (5 and 50 mM NaCl solution at flow rates of 4 and 8 m/d), the presence of n-dodecane/diesel in porous media could reduce the migration and enhance retention of A. lwoffii in quartz sand columns. Moreover, comparing with mutlicomponent NAPLs of n-dodecane, the monocomponent NAPLs (diesel) exhibited a greater reduction effect on the retention of A. lwoffii in porous media. Through systemically investigating the potential mechanisms via tracer experiment, visible chamber experiment, and theoretical calculation, we found that the reduction in porosity, repulsive forces and movement speeds, the presence of stagnant flow zones in porous media, particularly the biosurfactants generated by A. lwoffii contributed to the enhanced retention of bacteria in NAPL-contaminated porous media. Moreover, owing to presence of the greater amount of hydrophilic components in diesel than in n-dodecane, the available binding sites for the adsorption of bacteria were lower in diesel, resulting in the slightly decreased retention of A. lwoffii in porous media containing diesel than n-dodecane. This study demonstrated that comparing with porous media without NAPL contamination, the retention of strain capable of degrading NAPL in porous media with NAPL contamination was enhanced, beneficial for the subsequent biodegradation of NAPL.

Modeling Dissolution of Soluble Compounds from Multi-Component NAPL Using a Desorption Approximation.

Groundwater professionals require methods to estimate the potential time required to achieve remedial goals, including locations within and downgradient of zones containing non-aqueous phase liquids (NAPLs). NAPLs have long been recognized as persistent contaminant sources to groundwater. Dissolution of multi-component NAPLs is particularly complex, and numerical models that explicitly simulate it are not widely available. This study introduces an equilibrium partitioning approximation to simulate the dissolution of the most soluble chemical components from multi-component NAPL containing a significant fraction of relatively insoluble mass. The effective distribution coefficient that describes depletion of a specific compound from NAPL is estimated based on the properties of the NAPL and the porous medium. This study also presents numerical modeling results that support the utility of the method, with verification using published empirical data collected during dissolution of residual coal tar in a controlled laboratory sand tank experiment. The numerical modeling method uses equilibrium partitioning as an approximation and matched the concentrations of the two most soluble NAPL components in and downgradient of the NAPL zone with reasonable accuracy. The results suggest that the method should be useful for screening level assessments and can be adapted to compare relative groundwater restoration timeframes of select NAPL components for various remedial alternatives.

A review on dissolution of multi-component non-aqueous phase liquids: recent studies, mechanisms and mass transfer limitations

A review on dissolution of multi-component non-aqueous phase liquids: recent studies, mechanisms and mass transfer limitations

Persulfate Oxidation to Remediate Soil Contaminated by Weathered Multicomponent Non-Aqueous Phase Liquid: Column Experiments and Modeling

Persulfate Oxidation to Remediate Soil Contaminated by Weathered Multicomponent Non-Aqueous Phase Liquid: Column Experiments and Modeling

A mobile, modular and rapidly-acting treatment system for optimizing and improving the removal of non-aqueous phase liquids (NAPLs) in groundwater.

Non-aqueous phase liquids (NAPLs) in pumped groundwater are highly variable, challenging the selection of above-ground treatment strategies in pump-and-treat system. Adjustable systems with multiple treatment units are urgently required. In the present study, a mobile, modular and rapidly-acting treatment system was developed to treat groundwater contaminated by NAPLs at a chemical industrial site. The system integrated four units of coagulation sedimentation, air flotation, air stripping and chemical oxidation. During a 3-month onsite operation, the composition of groundwater NAPLs had huge fluctuations and different treatment units had unique advantages in eliminating some components. For instance, air stripping exhibited satisfactory removal efficiencies (>80%) for short-chain petroleum hydrocarbons and chloroalkanes, but poor performance for others comparing to other units. A decision-making tool and a central control system were further developed to combine and adjust the four units in proper orders, achieving satisfied removal efficiency (70-90%) for multi-component NAPLs, regardless of composition fluctuation. These findings raise the state-of-the-art modular and rapidly-acting groundwater treatment system to clean up NAPLs contaminated groundwater through pump-and-treat strategy, help in better understanding on the decision and management to improve the treatment performance, and provide guidelines for its implication at other sites contaminated with multi-component NAPLs or undergoing accidental contamination.

Intermediate-Scale Investigation of Enhanced-Solubilization Agents on the Dissolution and Removal of a Multicomponent Dense Nonaqueous Phase Liquid (DNAPL) Source

The presence of multicomponent nonaqueous phase liquid (NAPL) source zones in the subsurface can significantly complicate remediation efforts, transport predictions, and the development of accurate risk assessments. A series of flow-cell experiments was conducted to investigate the effectiveness of two different enhanced-solubilization agents for the removal of a multicomponent dense nonaqueous phase liquid (DNAPL) source zone from homogeneous porous media. The source zone consisted of an equal 1:1:1 mole mixture of cis-1,2-dichloroethene (DCE), trichloroethene (TCE), and tetrachloroethene (PCE) with NAPL saturation (Sn) targeted between 8 and 14 %. Solutions (5 wt%) of hydroxypropyl-β-cyclodextrin (HPCD) and sodium dodecyl sulfate (SDS) were flushed through the flow-cell system until nearly complete contaminant removal was achieved. Analysis of elution curves indicate that SDS was approximately 10 times more efficient at removing all three components from the system compared to HPCD. Although enhancement factor magnitudes vary for each specific contaminant component and enhanced-solubilization agent, the lowest-solubility contaminant component (i.e., PCE) consistently experienced the greatest relative solubility enhancement during flushing. SDS was generally superior when evaluated on a recovery basis; however, HPCD outperformed SDS for all contaminant components when compared based on moles-contaminant to moles-reagent removal efficiency analysis. Contaminant mass flux reduction analysis showed that enhanced-solubilization flushing (HPCD and SDS) resulted in general inefficient contaminant removal behavior. Raoult’s Law could be used to successfully predict aqueous contaminant concentrations from the multicomponent DNAPL source zone, indicating that dissolution processes were relatively ideal during both HPCD and SDS enhanced-solubilization flushing. These findings suggest that multicomponent NAPL source dissolution and removal depend upon the flushing agent itself and of the solubility and properties of the individual components of the NAPL mixture. The selection of a particular enhanced-flushing agent should be evaluated carefully prior to remediation as the dissolution, removal, and mass flux behavior of each component can vary significantly.

Laboratory study of non-aqueous phase liquid and water co-boiling during thermal treatment

In situ thermal treatment technologies, such as electrical resistance heating and thermal conductive heating, use subsurface temperature measurements in addition to the analysis of soil and groundwater samples to monitor remediation performance. One potential indication of non-aqueous phase liquid (NAPL) removal is an increase in temperature following observations of a co-boiling plateau, during which subsurface temperatures remain constant as NAPL and water co-boil. However, observed co-boiling temperatures can be affected by the composition of the NAPL and the proximity of the NAPL to the temperature measurement location. Results of laboratory heating experiments using single-component and multi-component NAPLs showed that local-scale temperature measurements can be mistakenly interpreted as an indication of the end of NAPL–water co-boiling, and that significant NAPL saturations (1% to 9%) remain despite observed increases in temperature. Furthermore, co-boiling of multi-component NAPL results in gradually increasing temperature, rather than a co-boiling plateau. Measurements of gas production can serve as a complementary metric for assessing NAPL removal by providing a larger-scale measurement integrated over multiple smaller-scale NAPL locations. Measurements of the composition of the NAPL condensate can provide ISTT operators with information regarding the progress of NAPL removal for multi-component sources.

Micellar solubilization of multi-component non-aqueous phase liquids (NAPLs) by Tween 80

Non-aqueous phase liquids (NAPLs) at contaminated sites often consist of multiple organic pollutants. In this study, the solubilization behavior of multi-component NAPLs was examined for the ternary mixtures of TCE-PCE-octane, PCE-o-xylene-octane, and hexane-octane-decane in Tween 80 solutions. In the TCE-PCE-octane mixtures, the most hydrophobic octane exhibited the enhanced solubilization compared with that predicted by the ideal behavior, but the least hydrophobic TCE showed the decreased solubilization. In reference to the ideal solubilization, PCE, the intermediate hydrophobic component in the mixtures, was less solubilized in an octane-rich region but more solubilized in a TCE-rich region. Similarly, in the PCE-o-xylene-octane mixtures, the relatively hydrophobic octane was preferentially solubilized, whereas the less hydrophobic PCE and o-xylene were outcompeted. The mutual effect on the solubilization between PCE and o-xylene was not significant due to the small difference in their hydrophobicity. Compared with the preceding NAPL mixtures, the hexane-octane-decane mixtures showed the lesser extent of the nonideal solubilization behavior, which might be attributed to the proximity in the hydrophobicity and molecular structure among these components. Thus, the nonideal solubilization behavior in NAPL mixtures was largely controlled by the relative hydrophobicity among NAPL components.

Multicomponent NAPL Source Dissolution: Evaluation of Mass-Transfer Coefficients

Mass transfer rate coefficients were quantified by employing an inverse modeling technique to high-resolution aqueous phase concentration data observed following an experimental release of a multicomponent nonaqueous phase liquid (NAPL) at a field site. A solute transport model (SEAM3D) was employed to simulate advective-dispersive transport over time coupled to NAPL dissolution. Model calibration was demonstrated by accurately reproducing the observed breakthrough times and peak concentrations at multiple observation points, observed mass discharge at pumping wells, and the reported mass depletions for three soluble NAPL constituents. Vertically variable NAPL mass transfer coefficients were derived for each constituent using an optimized numerical solute transport model, ranging from 0.082 to 2.0 day(-1) across all constituents. Constituent-specific coefficients showed a positive correlation with liquid-phase diffusion coefficients. Application of a time-varying mass transfer coefficient as NAPL mass depleted showed limited sensitivity during which over 80% of the most soluble NAPL constituent dissolved from the source. Long-term simulation results, calibrated to the experimental data and rendered in terms of mass discharge versus source mass depletion, exhibited multistage behavior.

Determination of the subcooled liquid solubilities of PAHs in partitioning batch experiments

Subcooled liquid solubility is the water solubility for a hypothetical state of liquid. It is an important parameter for multicomponent nonaqueous phase liquids (NAPLs) containing polycyclic aromatic hydrocarbons (PAHs), which can exist as liquids even though most of the solutes are solid in their pure form at ambient temperature. So far, subcooled liquid solubilities were estimated from the solid water solubility and fugacity ratio of the solid and (subcooled) liquid phase, but rarely derived from experimental data. In our study, partitioning batch experiments were performed to determine the subcooled liquid solubility of PAHs in NAPL-water system. For selected PAH, a series of batch experiments were carried out at increased mole fractions of the target component in the NAPL and at a constant NAPL/water volume ratio. The equilibrium aqueous PAH concentrations were measured with HPLC and/or GC-MS. The subcooled liquid solubility was derived by extrapolation of the experimental equilibrium aqueous concentration to a mole fraction of unity. With the derived subcooled liquid solubility, the fugacity ratio and enthalpy of fusion of the solute were also estimated. Our results show a good agreement between the experimentally determined and published data.

MODFLOW SURFACT: A State‐of‐the‐Art Use of Vadose Zone Flow and Transport Equations and Numerical Techniques for Environmental Evaluations

MODFLOW SURFACT is a state‐of‐the‐art simulator that utilizes vadose zone flow and transport equations to provide practical solutions to the analysis of flow and contaminant transport at various levels of complexity and sophistication as needed for site evaluation and closure. The variably saturated flow equation can be solved with standard retention functions or with bimodal or multimodal relative permeability curves for unsaturated flow in porous and fractured systems. The equation can further be solved with pseudo‐soil retention functions for confined–unconfined simulations and for use in wellbore hydraulics. Finally, the equation can be cast in terms of air phase flow to analyze subsurface air flow behavior. The variably saturated transport equation can be solved for an unsaturated medium or can be used for confined–unconfined situations. The passive phase of flow can be included in the equation to include both air and water phases in the transport situation. An immobile multicomponent nonaqueous phase liquid (NAPL) phase can further be included in the transport simulation with equilibrium partitioning providing mass transfer between phases, which adjusts NAPL saturations. Dual domain equations can be condensed into the transport equation to provide capabilities for analyzing transport in fractured media. General reaction capabilities provide analyses of complex environmental and geochemical interactions. Two examples are provided to demonstrate the value of a comprehensive simulation capability for site investigations.

Dissolution of polycyclic aromatic hydrocarbons from a non-aqueous phase liquid into a surfactant solution using a rotating disk apparatus

The mass transfer of two polycyclic aromatic hydrocarbons (PAHs), naphthalene and phenanthrene from a multicomponent non-aqueous phase liquid (NAPL) into a nonionic surfactant solution, Brij 35 was investigated using a rotating apparatus. Few experimental methods have been applied to the study of solubilization kinetics in organic liquids because in those systems, the interfacial area during mixing is more difficult to maintain and measure. This challenge was overcome by permeating the NAPL through a membrane. Mass transfer experiments were conducted in the absence and presence of surfactant, and the concentrations of naphthalene and phenanthrene in the bulk aqueous phase were determined in samples collected at different time intervals from the time of initial contact of the NAPL phase with the aqueous solution phase. Experiments in pure water demonstrated that the rotating apparatus behaves as in much the same way as the Levich's rotating disk. The mass transfer coefficients and the dissolution of PAHs into the surfactant solution were measured at different doses of Brij 35. As the surfactant concentration increased, the mass transfer coefficients for both PAHs from the NAPL decreased.

Analytical closed-form solutions for assessing pumping cycles, times, and costs required for NAPL remediation

An analytical solution is given to evaluate the number and duration of pumping cycles required for the remediation by pumping of contaminants, both single component and multi-component non-aqueous phase liquids (NAPLs), when no free product is present in the system. The method can be applied in a homogenous medium if the contamination zones have been delineated and residual total NAPL concentrations assessed. Based on the principle of the NAPL partitioning in unsaturated or saturated porous media, analytical closed-form solutions are provided for both cases of remediation by pumping in saturated and unsaturated conditions: “pump-and-treat” and “soil vapor extraction”. In each case we determine the number of pumping cycles required to reach the residual required concentration of NAPL (for example, according to health-based standards), considering one or more chemicals simultaneously present in an aquifer. The method requires information on the aquifer saturation state and the properties of the chemicals of interest. Calculations are based on the assumption of equilibrium partitioning of chemicals between the pore water, the soil solids, and the soil gas (in the case of unsaturated conditions), and no presence of a NAPL phase.

Permanganate Treatment of an Emplaced DNAPL Source

AbstractIn situ chemical oxidation (ISCO) using permanganate is one of the few promising technologies that have recently appeared with the capability of aggressively removing mass from nonaqueous phase liquid (NAPL) source zones. While NAPL mass in regions of the treatment zone where delivery is dominated by advection can be removed rather quickly, the rate of mass removal from stagnant zones is diffusion controlled. This gives rise to partial mass removal and a concomitant reduction in the NAPL mass, downgradient ground water concentrations, and the dissolution rate associated with the source zone. Therefore, monitoring the performance of a permanganate ISCO treatment system is important to maintain the desired efficiency and to establish a treatment end point. In this paper, we illustrate the use of various monitoring approaches to assess the performance of a pilot‐scale investigation that involved treatment of a multicomponent NAPL residual source zone with permanganate using a ground water recirculation system for 485 d. Ongoing treatment performance was assessed using permanganate and chloride concentration data obtained from extraction wells, 98 piezometers located approximately 1 m downgradient from the source, and ground water profiling. At the completion of treatment, 23 intact soil cores were extracted from the source zone and used to determine the remaining NAPL mass and manganese deposition. Based on the data collected, more than 99% of the initial NAPL mass was removed during treatment; however, remnant NAPL was sufficient to generate a small but measurable dissolved phase trichloroethene (TCE) and perchloroethene (PCE) plume. As a result of treatment, the ambient‐gradient discharge rates were reduced by 99% for TCE and 89% for PCE relative to baseline conditions. The lack of complete source zone oxidation was presumed to be the result of dissolution fingers, which channeled the permanganate solution through the source zone preventing direct contact with the NAPL and giving rise to diffusion‐limited mass removal.

Radon as a naturally occurring tracer for the assessment of residual NAPL contamination of aquifers

The noble gas radon has a strong affinity to non-aqueous phase-liquids (NAPLs). That property makes it applicable as naturally occurring partitioning tracer for assessing residual NAPL contamination of aquifers. In a NAPL contaminated aquifer, radon dissolved in the groundwater partitions preferably into the NAPL. The magnitude of the resulting radon deficit in the groundwater depends on the NAPL-specific radon partition coefficient and on the NAPL saturation of the pore space. Hence, if the partition coefficient is known, the NAPL saturation is attainable by determination of the radon deficit. After a concise discussion of theoretical aspects regarding radon partitioning into NAPL, related experimental data and results of a field investigation are presented. Aim of the laboratory experiments was the determination of radon partition coefficients of multi-component NAPLs of environmental concern. The on-site activities were carried out in order to confirm the applicability of the “radon method” under field conditions.

Dissolution of a multicomponent DNAPL pool in an experimental aquifer

This paper presents the results from a well-defined, circular-shaped, multicomponent dense nonaqueous phase liquid (DNAPL) pool dissolution experiment conducted in a three-dimensional, bench scale model aquifer. The multicomponent pool is a mixture of tetrachloroethylene (PCE) and 1,1,2-trichloroethane (1,1,2-TCA); PCE was the major component and 1,1,2-TCA was the minor component. Downgradient plume concentrations were measured at five specific locations over time until the majority of the 1,1,2-TCA was depleted from the DNAPL pool source. The experimental results suggest distinct spatial-temporal plume patterns for minor DNAPL components versus major DNAPL components. The downgradient concentration varied over time for 1,1,2-TCA while a stable plume developed for PCE. A semi-analytical solution for contaminant transport resulting from dissolution of multicomponent nonaqueous phase liquid pools successfully simulated the plume structure and dynamics for both the major and minor DNAPL components.

Modeling the transport of dissolved contaminants originating from a nonaqueous phase liquid source containing polycyclic aromatic hydrocarbon compounds in groundwater

A three-dimensional mathematical model is developed for simulating the transport of dissolved contaminants originating from a well-defined, multicomponent nonaqueous phase liquid (NAPL) source containing polycyclic aromatic hydrocarbon (PAH) compounds in groundwater. The dissolution process for each NAPL component is envisioned to occur in a successive series of small dissolution intervals (or pulses). The equilibrium aqueous phase concentration of each component and the source dimensions are assumed to remain constant for the duration of each dissolution interval. The model accounts for possible solidification of PAH components as the NAPL source dissolves. Aqueous phase contaminant concentrations resulting from each dissolution interval are calculated using an existing analytical solution. A synthetic PAH-rich NAPL mixture consisting of benzene and eight PAH components is used for model simulations. The model is useful for evaluation and prediction of downstream aqueous phase contaminant concentrations resulting from dissolution of a PAH-rich NAPL source. Key words: contaminant transport, groundwater, nonaqueous phase liquid (NAPL), mathematical modeling, polycyclic aromatic hydrocarbons.

Selective Solubilization of Polycyclic Aromatic Hydrocarbons from Multicomponent Nonaqueous-Phase Liquids into Nonionic Surfactant Micelles

This research investigates the equilibrium solubilization behavior of naphthalene and phenanthrene from multicomponent nonaqueous-phase liquids (NAPLs) by five different polyoxyethylene nonionic surfactants. The overall goal of the study was to achieve an improved understanding of surfactant-aided dissolution of polycyclic aromatic hydrocarbons (PAHs) from multicomponent NAPLs in the context of surfactant-enhanced remediation of contaminated sites. The extent of solubilization of the PAHs in the surfactant micelles increased linearly with the PAH mole fraction in the NAPL. The solubilization extent and micelle-water equilibrium partition coefficient of the PAHs increased with the size of the polar shell region of the micelles rather than the size of the hydrophobic core of the micelle. The presence of both PAHs in the shell region of the micelles was confirmed by 1H NMR analysis. This is an important observation because it is commonly assumed that in multi-solute systems the solutes with relatively greater hydrophobicity are solubilized only in the micellar core. A comparison of the 1H NMR spectra of pure surfactant solutions and solutions contacted with various NAPLs demonstrated that the distribution of PAHs between the shell and the core changed with the concentration of PAHs in the micelles and in the NAPL. Competitive solubilization of the PAHs was observed when both PAHs were present in the NAPL. For example, in surfactant solutions of Brij 35 and Tween 80, the solubilization of phenanthrene was decreased in the presence of naphthalene as compared to systems that contained phenanthrene as the only solute. In contrast, with micellar solutions of Tergitol NP-10 and Triton X-100, phenanthrene solubilization was enhanced in the presence of naphthalene. The activity coefficients of the PAHs in the micellar phase were generally found to increase with PAH concentrations in the micelle.

The role of interfacial films in the mass transfer of naphthalene from creosotes to water

Viscous, semi-rigid interfacial films that are formed at the interface of certain multi-component non-aqueous phase liquid (NAPLs) and water can significantly reduce the rates of mass transfer of solutes. Creosote–water systems were investigated for their ability to form interfacial films. The effects of these films on the creosote–water partition and on mass transfer of a representative solute, naphthalene, were investigated in a series of experiments. The area-independent mass transfer coefficient of naphthalene contained in creosote decreased by 30% over a 1-week period in systems containing creosote and water. Further aging for up to 21 days did not result in significant additional decreases in the mass transfer coefficient. The creosote–water partition coefficient, however, did not change with extended contact. The presence of viscous interfacial films in creosote–water systems was demonstrated in pendant drop tests. These interfacial films most likely caused the reduction in solute mass transfer coefficients by providing significant resistance to the diffusion of solutes through the interfacial film. Results from mass transfer experiments conducted under different system conditions suggested that hindered diffusion of naphthalene through the bulk creosote phase, changes in composition of creosote as a result of extended dissolution, or changes in creosote–water interfacial area did not contribute to the decrease in naphthalene mass transfer coefficient.

Acoustically enhanced multicomponent NAPL ganglia dissolution in water saturated packed columns.

The impact of acoustic pressure waves on multicomponent nonaqueous phase liquid (NAPL) ganglia dissolution in water saturated columns packed with glass beads was investigated. Laboratory data from dissolution experiments with two and three component NAPL mixtures suggested that acoustic waves significantly enhance ganglia dissolution due to the imposed oscillatory interstitial water velocity. The dissolution enhancement was shown to be directly proportional to the acoustic wave frequency. Furthermore, it was demonstrated that the greatest dissolution enhancement in the presence of acoustic waves is associated with the component of the NAPL mixture having the smallest equilibrium aqueous solubility. Finally, square shaped acoustic waves were shown to lead to greater NAPL dissolution enhancement compared to sinusoidal and triangular acoustic waves. The results of this study suggested that aquifer remediation using acoustic waves is a promising method particularly for aquifers contaminated with NAPLs containing components with very low equilibrium aqueous solubilities.