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1.
Nonaqueous phase liquid (NAPL) is a long-term source of ground water contamination as the pollutant slowly partitions into the air and water phases. The objective of this work was to study the efficacy of aqueous surfactant solution to enhance the dissolution of a residual NAPL below the capillary fringe, hence reducing the time needed for aquifer restoration. An analytical technique was developed to measure the concentration of NAPL in a nonionic surfactant. Soil column experiments simulated conditions in the saturated soil where a NAPL may become trapped as a discontinuous immobile phase. Experimental results indicate that dissolution was a rate-limited process, approaching equilibrium concentrations after 24 hours. The relative permeability of the aqueous phase initially decreased as surfactant was injected, but increased over time as the saturation of residual NAPL was reduced through mass transfer into the surfactant-enhanced aqueous phase. These findings suggest that enhancing the aqueous phase with a nonionic surfactant may significantly enhance the in situ recovery or residual NAPL.  相似文献   

2.
At a study site in the midwestern United States, multiple-completion wells demonstrated that a vertical hydraulic gradient was responsible for the contamination pattern exhibited by chlorinated solvent plumes. The typical pattern consisted of little or no contamination in the upper portion of the aquifer with concentrations increasing with depth. When ground water contamination was discovered in an unexpected portion of the site, water level elevations and contaminant distribution data obtained from multiple-completion wells resulted in identification of the source location. The well eventually determined to be located in the source area displayed contaminant levels much higher in the upper zone of the aquifer — the opposite contamination pattern of other on-site wells. Such results indicated that the spill had occurred near this location and that solvent residing along the capillary fringe was continuing to contaminate the aquifer.  相似文献   

3.
Neat ethanol (75.7 L) was released into the upper capillary zone in a continuous-flow, sand-packed aquifer tank (8.2 m3) with an average seepage velocity of 0.75 m/day. This model aquifer system contained a residual nonaqueous phase liquid (NAPL) that extended from the capillary zone to 10 cm below the water table. Maximum aqueous concentrations of ethanol were 20% v/v in the capillary zone and 0.08% in the saturated zone at 25 and 30 cm downgradient from the emplaced NAPL source, respectively. A bench-scale release experiment was also conducted for a similar size spill (scaled to the plan area). The concentrations of ethanol in ground water for both the bench- and pilot-scale experiments were consistent with advective–dispersive limited mass transfer from the capillary to the saturated zone. Concentrations of monoaromatic hydrocarbons and isooctane increased in the pore water of the capillary zone as a result of both redistribution of residual NAPL (confirmed by visualization) and enhanced hydrocarbon dissolution due to the cosolvent effect exerted by ethanol. In the tank experiment, higher hydrocarbon concentrations in ground water were also attributed to decreased hydrocarbon biodegradation activity caused by preferential microbial utilization of ethanol and the resulting depletion of oxygen. These results infer that spills of highly concentrated ethanol will be largely confined to the capillary zone due to its buoyancy, and ethanol concentrations in near-source zone ground water will be controlled by mass transfer limitations and hydrologic conditions. Furthermore, highly concentrated ethanol releases onto pre-existing NAPL will likely exacerbate impacts to ground water, due to NAPL mobilization and dissolution, and decreased bioattenuation of hydrocarbons.  相似文献   

4.
In this study, a water‐air two‐phase flow model was employed to investigate the formation, extension, and dissipation of groundwater ridging induced by recharge events in a hypothetical hillslope‐riparian zone, considering interactions between the liquid and gas phases in soil voids. The simulation results show that, after a rain begins, the groundwater table near the stream is elevated instantaneously and significantly, thereby generating a pressure gradient driving water toward both the stream (the discharge of groundwater to the stream) and upslope (the extension of groundwater ridging into upslope). Meanwhile, the airflow upslope triggered by the advancing wetting front moves downward gradually. Therefore, the extension of groundwater ridging into upslope and the downward airflow interact within a certain region. After the rain stops, groundwater ridging near the stream declines quickly while the airflow in the lower part of upslope is still moving into the hillslope. Thus, the airflow upslope mitigates the dissipation of groundwater ridging. Additionally, the development of groundwater ridging under different conditions, including rain intensity, intrinsic permeability, capillary fringe height, and initial groundwater table, was analyzed. Changes in intrinsic permeability affect the magnitude of groundwater ridging near the stream, as well as the downward speed of airflow, thereby generating highly complex responses. The capillary fringe is not a controlling factor but an influence factor on the formation of groundwater ridging, which is mainly related to the antecedent moisture. It was demonstrated that groundwater ridging also occurs where an unsaturated zone occurs above the capillary fringe with a subsurface lateral flow.  相似文献   

5.
The objective of this study was to investigate whether 222Rn in groundwater can be used as a tracer for light non‐aqueous phase liquid (LNAPL) quantification at a field site treated by dual‐phase LNAPL removal. After the break of a pipeline, 5 ha of soil in the nature reserve Coussouls de Crau in southern France was contaminated by 5100 m3 of crude oil. Part of this oil seeped into the underlying gravel aquifer and formed a floating oil body of about 3.9 ha. The remediation consists of plume management by hydraulic groundwater barriers and LNAPL extraction in the source zone. 222Rn measurements were performed in 21 wells in and outside the source zone during 15 months. In uncontaminated groundwater, the radon activity was relatively constant and remained always >11 Bq/L. The variability of radon activity measurements in wells affected by the pump‐and‐skim system was consistent with the measurements in wells that were not impacted by the system. The mean activities in wells in the source zone were, in general, significantly lower than in wells upgradient of the source zone, owing to partitioning of 222Rn into the oil phase. The lowest activities were found in zones with high non‐aqueous phase liquid (NAPL) recovery. LNAPL saturations around each recovery well were furthermore calculated during a period of high groundwater level, using a laboratory‐determined crude oil–water partitioning coefficient of 38.5 ± 2.9. This yielded an estimated volume of residual crude oil of 309 ± 93 m3 below the capillary fringe. We find that 222Rn is a useful and cheap groundwater tracer for finding zones of good LNAPL recovery in an aquifer treated by dual‐phase LNAPL removal, but that quantification of NAPL saturation using Rn is highly uncertain.  相似文献   

6.
After the initiation of gravity drainage, water is often assumed to be either (a) draining under unit gradient, or (b) at capillary/gravity equilibrium. Both of these simplifications can be useful, but the regimes of validity of each assumption must be delineated. Water pressures are measured versus time and distance as water drains out of a 1.6 m long sand column to determine the relative effects of capillary and gravitational forces during drainage. For medium sized sands (0.15–0.3 mm in diameter), the capillary pressure is constant in space in a large region of the column for over 12 days, and the water continues to flow under unit gradient for relatively long time scales. Similar results are seen for finer sands, but with a much faster approach to equilibrium. Numerical simulations and analytical estimates are presented and compare favorably to the measurements. Together, the experimental, theoretical and analytical results are used to calculate when capillary/gravity equilibrium is reached as a function of porous media properties and length of the unsaturated zone. The ratio of the length of the unsaturated zone to the bubbling pressure is a key parameter in determining the drainage regime, and that even for relatively short unsaturated zones the equilibrium time scale can be on the order of years.  相似文献   

7.
Behavior of gasoline pools following a denatured ethanol spill   总被引：1，自引：0，他引：1  
In 1999, approximately 72 m3 of denatured fuel-grade ethanol spilled at a bulk fuel terminal that had existing contamination within the subsurface. An unanticipated increase in the measured depth of the light nonaqueous phase liquid (LNAPL) was observed in nearby monitoring wells following the spill. This paper presents results of a laboratory analysis designed to understand the apparent increase in LNAPL mobility at this site. The two-dimensional stainless steel and glass tank allowed visual assessment of the potential effects that the addition of denatured ethanol may have on a site with pre-existing gasoline contamination. Digital images of gasoline and ethanol spill experiments were analyzed for changes in the characteristics of the existing gasoline pool and residual gasoline saturation in the unsaturated zone. Reductions in the surface and interfacial tensions resulted in significant changes in the size, shape, and saturation of the gasoline pool after the addition of ethanol to the system. The final gasoline pool occupied a smaller area and had a higher saturation. In addition, some smearing of the gasoline into the saturated zone occurred as the capillary fringe was depressed.  相似文献   

8.
The hydraulic gradient between aquifers and rivers is one of the most variable properties in a river/aquifer system. Detailed process understanding of bank storage under hydraulic gradients is obtained from a two‐dimensional numerical model of a variably saturated aquifer slice perpendicular to a river. Exchange between the river and the aquifer occurs first at the interface with the unsaturated zone. The proportion of total water exchanged through the river bank compared to the river bed is a function of aquifer hydraulic conductivity, partial penetration, and hydraulic gradient. Total exchange may be estimated to within 50% using existing analytical solutions provided that unsaturated zone processes do not strongly influence exchange. Model‐calculated bank storage is at a maximum when no hydraulic gradient is present and increases as the hydraulic conductivity increases. However, in the presence of a hydraulic gradient, the largest exchange flux or distance of penetration does not necessarily correspond to the highest hydraulic conductivity, as high hydraulic conductivity increases the components of exchange both into and out of an aquifer. Flood wave characteristics do not influence ambient groundwater discharge, and so in large floods, hydraulic gradients must be high to reduce the volume of bank storage. Practical measurement of bank storage metrics is problematic due to the limitations of available measurement technologies and the nested processes of exchange that occur at the river‐aquifer interface. Proxies, such as time series concentration data in rivers and groundwater, require further development to be representative and quantitative.  相似文献   

9.
The generation of vapor‐phase contaminant plumes within the vadose zone is of interest for contaminated site management. Therefore, it is important to understand vapor sources such as non‐aqueous‐phase liquids (NAPLs) and processes that govern their volatilization. The distribution of NAPL, gas, and water phases within a source zone is expected to influence the rate of volatilization. However, the effect of this distribution morphology on volatilization has not been thoroughly quantified. Because field quantification of NAPL volatilization is often infeasible, a controlled laboratory experiment was conducted in a two‐dimensional tank (28 cm × 15.5 cm × 2.5 cm) with water‐wet sandy media and an emplaced trichloroethylene (TCE) source. The source was emplaced in two configurations to represent morphologies encountered in field settings: (1) NAPL pools directly exposed to the air phase and (2) NAPLs trapped in water‐saturated zones that were occluded from the air phase. Airflow was passed through the tank and effluent concentrations of TCE were quantified. Models were used to analyze results, which indicated that mass transfer from directly exposed NAPL was fast and controlled by advective‐dispersive‐diffusive transport in the gas phase. However, sources occluded by pore water showed strong rate limitations and slower effective mass transfer. This difference is explained by diffusional resistance within the aqueous phase. Results demonstrate that vapor generation rates from a NAPL source will be influenced by the soil water content distribution within the source. The implications of the NAPL morphology on volatilization in the context of a dynamic water table or climate are discussed.  相似文献   

10.
Soil-gas surveys are becoming more widely accepted as a tool for the preliminary determination of the extent of soil and ground water contamination by volatile organic compounds (VOCs). The interpretation of the results of published soil-gas surveys has been necessarily limited and qualitative due to a lack of adequate models. There has been considerable effort in the recent past to characterize the transport and fate of pesticides in soil. However, the behavior of pesticides generally differ substantially from those of VOCs.
This paper presents a computer model developed to simulate the diffusive transport of VOC vapor through unsaturated soils using a two-dimensional, finite-difference, solution to Fick's second law of diffusion. An effective diffusion coefficient that incorporates the effects of tortuosity, moisture content, and soil organic carbon content is computed. Although the model has not been validated due to the unavailability of adequate field or laboratory data, nevertheless, sensitivity analyses demonstrate the importance of soil moisture and, secondarily, organic matter content in controlling the migration of VOC vapor through the unsaturated zone. The interpretation of soil-gas surveys can be complicated by unknown spatial heterogeneities in soil moisture and organic carbon content, temporal variations in moisture content, extent of contaminant migration as a non-aqueous phase liquid and by the unknown extent of VOC liquid and contaminated ground water.  相似文献   

11.
This paper presents model simulation results of vapor intrusion into structures built atop sites contaminated with volatile or semivolatile chemicals of concern. A three-dimensional finite element model was used to investigate the importance of factors that could influence vapor intrusion when the site is characterized by nonhomogeneous soils. Model simulations were performed to examine how soil layers of differing properties alter soil-gas concentration profiles and vapor intrusion rates into structures. The results illustrate difference in soil-gas concentration profiles and vapor intrusion rates between homogeneous and layered soils. The findings support the need for site conceptual models to adequately represent a site's geology when conducting site characterizations, interpreting field data, and assessing the risk of vapor intrusion at a given site. For instance, in layered geologies, a lower permeability and diffusivity soil layer between the source and building often limits vapor intrusion rates, even if a higher permeability layer near the foundation permits increased soil-gas flow rates into the building. In addition, the presence of water-saturated clay layers can considerably influence soil-gas concentration profiles. Therefore, interpreting field data without accounting for clay layers in the site conceptual model could result in inaccurate risk calculations. Important considerations for developing more accurate conceptual site models are discussed in light of the findings.  相似文献   

12.
The spatial distribution of residual light non-aqueous phase liquid (LNAPL) is an important factor in reactive solute transport modeling studies. There is great uncertainty associated with both the areal limits of LNAPL source zones and smaller scale variability within the areal limits. A statistical approach is proposed to construct a probabilistic model for the spatial distribution of residual NAPL and it is applied to a site characterized by ultra-violet-induced-cone-penetration testing (CPT–UVIF). The uncertainty in areal limits is explicitly addressed by a novel distance function (DF) approach. In modeling the small-scale variability within the areal limits, the CPT–UVIF data are used as primary source of information, while soil texture and distance to water table are treated as secondary data. Two widely used geostatistical techniques are applied for the data integration, namely sequential indicator simulation with locally varying means (SIS–LVM) and Bayesian updating (BU). A close match between the calibrated uncertainty band (UB) and the target probabilities shows the performance of the proposed DF technique in characterization of uncertainty in the areal limits. A cross-validation study also shows that the integration of the secondary data sources substantially improves the prediction of contaminated and uncontaminated locations and that the SIS–LVM algorithm gives a more accurate prediction of residual NAPL contamination. The proposed DF approach is useful in modeling the areal limits of the non-stationary continuous or categorical random variables, and in providing a prior probability map for source zone sizes to be used in Monte Carlo simulations of contaminant transport or Monte Carlo type inverse modeling studies.  相似文献   

13.
The diffusion of 2,2,4-trimethylpentane (TMP) and 2,2,5-trimethylhexane (TMH) vapors put of residually contaminated sandy soil from the U.S. Environmental Protection Agency (EPA) field research site at Traverse City, Michigan, was measured and modeled. The headspace of an intact core sleeve sample was swept with nitrogen gas to simulate the diffusive release of hydrocarbon vapors from residual aviation gasoline in and immediately above the capillary fringe to a soil-venting air flow in the unsaturated zone. The resulting steady-state profile was modeled using existing diffusivity and air porosity estimates in a balance of diffusive flux and a first order source term. The source strength, which was calibrated with the observed flux of 2,2,4-TMP leaving the sleeve, varied with the residual gasoline remaining in the core, but was independent of the headspace sweep flow rate. This finding suggested that lower soil-venting air flow rates were in principle as effective as higher air flow rates in venting LNAPL vapors from contaminated soils. The saturated vapor concentration ratio of 2,2,4-TMP to 2,2,5-TMH decreased from 6.6 to 3.5 over the duration of the experiments in an expression of distillation effects. The vertical profile model was tested against sample port data in four separate experiments for both species, yielding mean errors ranging from 0 to—24 percent in magnitude.  相似文献   

14.
The point velocity probe (PVP) is a device that can measure groundwater velocity at the centimeter scale, and unlike devices that measure velocity within well screens, the PVP operates while in direct contact with the porous medium. Because of this feature, it was postulated that the PVP could be effective in measuring velocity within the capillary fringe. This hypothesis was tested using a laboratory flow-through cell filled with a medium-fine sand from Canadian Forces Base Borden. The cell was constructed to simulate conditions such that the PVP was positioned from 2.5 cm below the water table to 79 cm above the water table. As the water table was lowered, the PVP gave highly consistent values of velocity over the range equivalent to 2.5 cm below the water table to 44 cm above the water table, the approximate extent of the capillary fringe. The average measured velocity was 11.3 cm/d ± 11.6%, somewhat higher than that calculated based on the measured discharge through the cell (7.5 cm/d ± 5.5%). With a further decline in the water table there was a progressive decrease in the measured velocity values, consistent with the declining hydraulic conductivity as the sand material drained. Readings could not be made beyond about 57 cm, where the water content was approximately 75% of saturation. These experiments showed that the PVP is capable of measuring groundwater velocity within the saturated zone above the water table and possibly into the unsaturated zone. Currently, this is the only instrument available with this capability.  相似文献   

15.
Abstract

Wetting front instability (fingered flow) accelerates solute transport through the unsaturated zone to the groundwater table. Whether fingers widen or dissipate close to the groundwater is unclear. Water flow in a two-dimensional artificial capillary fringe below a dry layer exhibiting fingered flow was investigated. The flow diverged strongly in the wet soil, suggesting that fingers dissipate. Expressions for the finger radius in dry and wet soil were combined and adapted to a soil hydraulic property parameterization popular in numerical modelling. The modified equation provided finger radii for soils in humid and arid climates. The fingers in the arid soil were excessively wide. The finger radii were used to model solute transport, assuming fingers dissipated in the subsoil. Modelling was cumbersome for the arid climate. One shower may often be insufficient to trigger fingering in arid regions with short, heavy showers. In soils with shallow groundwater, the diverging subsoil flow determines solute leaching.  相似文献   

16.
Soil gas samples from intact soil cores were collected on adsorbents at a field site, then thermally desorbed and analyzed by laboratory gas chromatography (GC). Vertical concentration profiles of predominant vapor phase petroleum hydrocarbons under ambient conditions were obtained for the zone directly above the capillary fringe. Water and residual phase weathered aviation gasoline were present in this region of the profile.
The sampling, trapping, and GC methodology was effective in most respects. Reproducibility, trapping, and desorption efficiency were generally satisfactory, and different sorbent tubes gave similar results. A minor shortcoming of the method occurred with the most volatile compound, 2,3-dimcthylbutane, which was poorly retained during several weeks of storage lime and was also poorly desorbed.
Vapor phase concentrations of predominant hydrocarbon compounds all increased with depth at one sampling location. At a more highly contaminated location, concentrations of highly volatile compounds increased with depth while concentrations of less volatile compounds remained constant or decreased, possibly indicating distillation effects. Scatier in the data was attributed to heterogeneities in water and residual phase distribution.  相似文献   

17.
Subslab or shallow soil-gas data are often compared with indoor air concentration data in vapor intrusion (VI) evaluations. If no indoor air data are available or confounding sources are present, or if future scenarios are considered, the soil-gas data may be used to estimate the indoor air concentrations due to VI. The typical approach in risk assessments is to use the 95th percentile values from a set of concentration data. For VI studies, however, this rarely is an option because the data sets tend to be quite small. Therefore, various guidance documents urge the use of maximum soil-gas values. This may be reasonable for small residential buildings, but can lead to very conservatively biased estimates if applied to large industrial buildings with localized areas of contamination, especially given that the sampling locations may not be randomly selected and instead are biased toward worst-case locations. By this approach, VI guidance implicitly tolerates a large percentage of false positive decision errors to minimize the number of false negative decision errors. In this paper, implications of using maximum values are discussed and illustrated with data sets from a number of large industrial buildings at various sites. An alternative approach to using maximum soil-gas values is proposed that serves to reduce the number of false positive results while controlling the number of false negatives to an acceptable level.  相似文献   

18.
Flow of nonvolatile nonaqueous phase liquid (NAPL) and aqueous phases that account for mobile, entrapped, and residual NAPL in variably saturated water-wet porous media is modeled and compared against results from detailed laboratory experiments. Residual saturation formation in the vadose zone is a process that is often ignored in multifluid flow simulators, which might cause an overestimation of the volume of NAPL that reaches the ground water. Mobile NAPL is defined as being continuous in the pore space and flows under a pressure gradient or gravitational body force. Entrapped NAPL is defined as being occluded by the aqueous phase, occurring as immobile ganglia surrounded by aqueous phase in the pore space and formed when NAPL is replaced by the aqueous phase. Residual NAPL is defined as immobile, nonwater entrapped NAPL that does not drain from the pore spaces and is conceptualized as being either continuous or discontinuous. Free NAPL comprises mobile and residual NAPL. The numerical model is formulated on mass conservation equations for oil and water, transported via NAPL and aqueous phases through variably saturated porous media. To account for phase transitions, a primary variable switching scheme is implemented for the oil-mass conservation equation over three phase conditions: (1) aqueous or aqueous-gas with dissolved oil, (2) aqueous or aqueous-gas with entrapped NAPL, and (3) aqueous or aqueous gas with free NAPL. Two laboratory-scale column experiments are modeled to verify the numerical model. Comparisons between the numerical simulations and experiments demonstrate the necessity to include the residual NAPL formation process in multifluid flow simulators.  相似文献   

19.
We performed quasi‐two‐dimensional flow through laboratory experiments to study the effect of a coarse‐material inclusion, located in the proximity of the water table, on flow and oxygen transfer in the capillary fringe. The experiments investigate different phases of mass transfer from the unsaturated zone to anoxic groundwater under both steady‐state and transient flow conditions, the latter obtained by fluctuating the water table. Monitoring of flow and transport in the different experimental phases was performed by visual inspection of the complex flow field using a dye tracer solution, measurement of oxygen profiles across the capillary fringe, and determination of oxygen fluxes in the effluent of the flow‐through chamber. Our results show significant effects of the coarse‐material inclusion on oxygen transfer during the different phases of the experiments. At steady state, the oxygen flux across the unsaturated/saturated interface was considerably enhanced due to flow focusing in the fully water‐saturated coarse‐material inclusion. During drainage, a zone of higher water saturation formed in the fine material overlying the coarse lens. The entrapped oxygen‐rich aqueous phase contributed to the total amount of oxygen supplied to the system when the water table was raised back to its initial level. In case of imbibition, pronounced air entrapment occurred in the coarse lens, causing oxygen to partition between the aqueous and gaseous phases. The oxygen mass supplied to the anoxic groundwater following the imbibition event was found to be remarkably higher (approximately seven times) in the heterogeneous system compared with a similar experiment performed in a homogeneous porous medium.  相似文献   

20.
Evaluation of volatilization as a natural attenuation pathway for MTBE   总被引：2，自引：0，他引：2  
Lahvis MA  Baehr AL  Baker RJ 《Ground water》2004,42(2):258-267
Volatilization and diffusion through the unsaturated zone can be an important pathway for natural attenuation remediation of methyl tert-butyl ether (MTBE) at gasoline spill sites. The significance of this pathway depends primarily on the distribution of immiscible product within the unsaturated zone and the relative magnitude of aqueous-phase advection (ground water recharge) to gaseous-phase diffusion. At a gasoline spill site in Laurel Bay, South Carolina, rates of MTBE volatilization from ground water downgradient from the source are estimated by analyzing the distribution of MTBE in the unsaturated zone above a solute plume. Volatilization rates of MTBE from ground water determined by transport modeling ranged from 0.0020 to 0.0042 g m(-2)/year, depending on the assumed rate of ground water recharge. Although diffusive conditions at the Laurel Bay site are favorable for volatilization, mass loss of MTBE is insignificant over the length (230 m) of the solute plume. Based on this analysis, significant volatilization of MTBE from ground water downgradient from source areas at other sites is not likely. In contrast, model results indicate that volatilization coupled with diffusion to the atmosphere could be a significant mass loss pathway for MTBE in source areas where residual product resides above the capillary zone. Although not documented, mass loss of MTBE at the Laurel Bay site due to volatilization and diffusion to the atmosphere are predicted to be two to three times greater than mass loading of MTBE to ground water due to dissolution and recharge. This result would imply that volatilization in the source zone may be the critical natural attenuation pathway for MTBE at gasoline spill sites, especially when considering capillary zone limitations on volatilization of MTBE from ground water and the relative recalcitrance of MTBE to biodegradation.  相似文献   

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