Simulating the fate and transport of TCE from groundwater to indoor air

This work provides an exploratory analysis on the relative importance of various factors controlling the fate and transport of volatile organic contaminants (in this case, TCE) from a DNAPL source zone located below the water table and into the indoor air. The analysis is conducted using the multi-phase compositional model CompFlow Bio, with the base scenario problem geometry reminiscent of a field experiment conducted by Rivett [Rivett, M.O., (1995), Soil–gas signatures from volatile chlorinated solvents: Borden field experiments. Groundwater, 33(1), 84–98.] at the Borden aquifer where groundwater was observed to transport a contaminant plume a substantial distance without vertical mass transport of the contaminant across the capillary fringe and into the vadose zone. Results for the base scenario model indicate that the structure of the permeability field was largely responsible for deflecting the groundwater plume upward towards the capillary fringe, permitting aqueous phase diffusion to transport the TCE into the vadose zone. Alternative permeability realizations, generated as part of a Monte Carlo simulation process, at times deflected the groundwater plume downwards causing the extended thickness of the saturated zone to insulate the vadose zone from exposure to the TCE by upward diffusive transport. Comparison of attenuation coefficients calculated using the CompFlow Bio and Johnson and Ettinger [Johnson, P.C. and Ettinger, R.A., (1991), Heuristic model for predicting the intrusion rate of contaminant vapors into buildings. Environmental Science and Technology, 25, 1445–1452.] heuristic model exhibited fortuitous agreement for the base scenario problem geometry, with this agreement diverging for the alternative permeability realizations as well as when parameters such as the foundation slab fracture aperture, the indoor air pressure drop, the capillary fringe thickness, and the infiltration rate were varied over typical ranges.     

Oxygenated gasoline release in the unsaturated zone - Part 1: Source zone behavior

Oxygenates present in gasoline, such as ethanol and MTBE, are a concern in subsurface contamination related to accidental spills. While gasoline hydrocarbon compounds have low solubility, MTBE and ethanol are more soluble, ethanol being completely miscible with water. Consequently, their fate in the subsurface is likely to differ from that of gasoline. To evaluate the fate of gasoline containing oxygenates following a release in the unsaturated zone shielded from rainfall/recharge, a controlled field test was performed at Canadian Forces Base Borden, in Ontario. 200L of a mixture composed of gasoline with 10% ethanol and 4.5% MTBE was released in the unsaturated zone, into a trench 20cm deep, about 32cm above the water table. Based on soil cores, most of the ethanol was retained in the source, above the capillary fringe, and remained there for more than 100 days. Ethanol partitioned from the gasoline to the unsaturated pore-water and was retained, despite the thin unsaturated zone at the site (~35cm from the top of the capillary fringe to ground surface). Due to its lower solubility, most of the MTBE remained within the NAPL as it infiltrated deeper into the unsaturated zone and accumulated with the gasoline on top of the depressed capillary fringe. Only minor changes in the distribution of ethanol were noted following oscillations in the water table. Two methods to estimate the capacity of the unsaturated zone to retain ethanol are explored. It is clear that conceptual models for sites impacted by ethanol-fuels must consider the unsaturated zone.     

Changes in air saturation and air-water interfacial area during surfactant-enhanced air sparging in saturated sand

Reduction in the surface tension of groundwater, prior to air sparging for removal of volatile organic contaminant from aquifer, can greatly enhance the air content and the extent of influence when air sparging is implemented. However, detailed information on the functional relationship between water saturation, air-water contact area induced by air sparging and the surface tension of water has not been available. In this study, the influence of adding water-soluble anionic surfactant (sodium dodecyl benzene sulfonate) into groundwater before air sparging on the air-water interfacial area and water saturation was investigated using a laboratory-scale sand packed column. It was found that water saturation decreases with decreasing surface tension of water until it reaches a point where this trend is reversed so that water saturation increases with further decrease in the surface tension. The lowest water saturation of 0.58 was achieved at a surface tension of 45.4 dyn/cm, which is considered as the optimum surface tension for maximum de-saturation for the initially water-saturated sand used in this study. The air-water contact area generated in the sand column due to air sparging was measured using a gaseous interfacial tracer, n-decane, and was found to monotonically increase with decreasing water saturation. The results of this study provide useful design information for surfactant-enhanced air sparging removal of volatile contaminants from aquifers.     

Full and boundary-layer solutions of the steady air sparging problem

The one previous analytical solution to the steady sparging problem in a homogeneous soil was in the boundary-layer approximation that neglects the vertical capillary pressure gradient. The present study gives an analytical solution to the full air-flow equation, with the corresponding boundary-layer solution for comparison. The full solution predicts sparging below the air-injection point, whereas the boundary-layer solution does not. Solutions are expressed both in terms of the dimensionless Kirchhoff potential θ (increasing monotonically with capillary pressure and air saturation also) and the dimensionless Stokes stream function F (mapping the pattern of air flow). Both θ and F show the full solution predicting more effective sparging near the injection point than does the boundary-layer solution. The overall boundary-layer relative error, however, decreases as dimensionless air-injection depth below the undisturbed water-table increases.     

Modeling of air sparging of VOC-contaminated soil columns

Air sparging is a remediation technology currently being applied for the restoration of sites contaminated with volatile organic compounds (VOCs). Attempts have been made by various researchers to model the fate of VOCs in the gas and liquid phase during air sparging. In this study, a radial diffusion model with an air–water mass transfer boundary condition was developed and applied for the prediction of VOC volatilization from air sparging of contaminated soil columns. The approach taken was to use various parameters such as mass transfer coefficients and tortuosity factors determined previously in separate experiments using a single air channel apparatus and applying these parameters to a complex system with many air channels. Incorporated in the model, is the concept of mass transfer zone (MTZ) where diffusion of VOCs in this zone was impacted by the volatilization of VOCs at the air–water interface but with negligible impact outside the zone. The model predicted fairly well the change in the VOC concentrations in the exhaust air, the final average aqueous VOC concentration, and the total mass removed. The predicted mass removal was within 1% to 20% of the actual experimental mass removed. The results of the model seemed to suggest that air-sparged soil columns may be modeled as a composite of individual air channels surrounded by a MTZ. For a given air flow rate and air saturation, the VOC removal was found to be inversely proportional to the radius of the air channel. The approach taken provided conceptual insights on mass transfer processes during air sparging operations.     

鼠李糖脂促进地下水苯和氯苯污染的空气喷射修复

通过一维砂柱室内模拟实验,研究生物表面活性剂鼠李糖脂对空气喷射修复地下水中苯和氯苯污染的促进作用。实验研究了水中表面张力的变化对曝气过程中空气饱和度的影响,结果发现,在一定范围内,随着表面张力的下降,空气饱和度有大幅度的增加,当表面张力下降到37.75 mN/m以后,空气饱和度基本不再上升。曝气流量固定为300 mL/min,当地下水的表面张力由71.65 mN/m降到29.25 mN/m时,对应地下水中空气饱和度可由9.21%提高到20.1%。污染物去除实验的结果表明,添加低浓度的鼠李糖脂可以环保高效地提高苯和氯苯的去除量以及去除速率。因此,添加鼠李糖脂可以作为一种有效的强化方法来提高空气喷射法去除地下水中苯和氯苯污染的效率。     

Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

A field trial to assess the performance of CO2-supersaturated water injection for residual volatile LNAPL recovery

A pilot scale field trial was conducted to evaluate the recovery of volatile, light non-aqueous phase liquids (LNAPLs) using a novel remediation method termed supersaturated water injection (SWI). SWI uses a patented technology to efficiently dissolve high concentrations of CO₂ into water at elevated pressures. This water is injected into the subsurface resulting in the nucleation of CO₂ bubbles at and away from the injection point. The nucleating bubbles coalesce, rise and volatilize residual LNAPL ganglia. In this study, an LNAPL composed of 103 kg of volatile pentane and hexane, and 30 kg of non-volatile Soltrol was emplaced below the water table at residual saturation. The SWI technology removed 78% of the pentane and 50% of the less volatile hexane. Contaminant mass was still being removed when the system was shut down for practical reasons. The mass removed is comparable to that expected for air sparging but a much smaller volume of gas was injected using the SWI system.     

Comparison of physical technologies for biomass control in biofilters treating gaseous toluene

Excessive accumulation of biomass within gas-phase biofilters often results in the deterioration of removal performance. Compared with chemical and biological technologies, physical technologies are more effective in removing biomass and inducing less inhibition of the biofilter performance. This study applied different physical technologies, namely, air sparging, mechanical mixing, and washing with water at various temperatures, to remove excess biomass in biofilters treating toluene. Filter pressure drop, removed dry biomass, biofilter performance, and microbial metabolic characteristics were analyzed to evaluate the effectiveness of the methods. Results showed that air sparging was inefficient for biomass removal (1 kg dry biomass/m³ filter), whereas mechanical mixing significantly inhibited removal efficiencies (<30%). Washing of the packing with fluids was feasible, and hot fluids can remove a large amount of biomass. However, hot fluids reduce microbial activity and inhibit removal performance. Washing of the packing with either 20°C or 50°C water showed efficiency as >3 kg dry biomass/m³ filter can be removed at both temperatures with removal efficiencies at approximately 40% after treatment. Finally, different technologies were compared and summarized to propose an optimized strategy of biomass control for industrial biofilters.

Implications: This study is to apply different physical technologies, namely, air sparging, mechanical mixing, and washing with water of different temperatures, to remove the excess biomass in biofilters treating toluene. The filter pressure drop, removed dry biomass, biofilter performance, and microbial metabolic characteristics were all analyzed to evaluate the effectiveness of the methods. The results of this study provide useful information regarding biomass control of industrial biofilters.     

One-at-a-time sensitivity analysis of pollutant loadings to subsurface properties for the assessment of soil and groundwater pollution potential

Chemical leak was numerically simulated for four chemical substances: benzene (light non-aqueous phase liquid (NAPL)), tetrachloroethylene (dense NAPL), phenol (soluble in water), and pentachlorophenol (white crystalline solid) in a hypothetical subsurface leak situation using a multiphase compositional transport model. One metric ton of chemical substances was assumed to leak at a point 3.51 m above the water table in a homogeneous unconfined aquifer which had the depth to water table of 7.135 m, the hydraulic gradient of 0.00097, the recharge rate of 0.7 mm/day, and the permeability of 2.92?×?10^?10 m². For comparison, surface spill scenarios, which had a long pathway from source to the water table, were simulated. Using the model results, point-source pollutant loadings to soil and groundwater were calculated by multiplying mass, impact area, and duration above and below the water table respectively. Their sensitivity to subsurface properties (depth to water table, recharge rate, porosity, organic carbon content, decay rate, hydraulic gradient, capillary pressure, relative permeability, permeability) was analyzed, with changing each parameter within acceptable ranges. The study result showed that the pollutant loading to groundwater was more sensitive to the subsurface properties than the pollutant loading to soil. Decay rate, groundwater depth, hydraulic gradient and porosity were influential to pollutant loadings. The impact of influential parameters on pollutant loadings was nonlinear. The dominant subsurface properties of pollution loadings (e.g., decay rate, groundwater depth, hydraulic gradient, and porosity for groundwater) also affect the vulnerability, and the subsurface pollutant loadings defined in this study are dependent on chemical properties as well, which indicates that the influential hydrogeological and physicochemical parameters to pollutant loadings can be used for pollution potential assessment. The contribution of this work is the suggestion that the sensitivity of pollutant loadings can be used for pollution potential assessment. Soil and groundwater pollution potential of chemicals are discussed altogether for leak scenarios. A physics-based model is used to understand the impact of subsurface properties on the fate and transport of chemicals above and below the water table, and consequently their impact on the pollutant loading to soil and groundwater.

     

The effect of surface-active solutes on water flow and contaminant transport in variably saturated porous media with capillary fringe effects

Organic contaminants that decrease the surface tension of water (surfactants) can have an effect on unsaturated flow through porous media due to the dependence of capillary pressure on surface tension. We used an intermediate-scale 2D flow cell (2.44 x 1.53 x 0.108 m) packed with a fine silica sand to investigate surfactant-induced flow perturbations. Surfactant solution (7% 1-butanol and dye tracer) was applied at a constant rate at a point source located on the soil surface above an unconfined synthetic aquifer with ambient groundwater flow and a capillary fringe of approximately 55 cm. A glass plate allowed for visual flow and transport observations. Thirty instrumentation stations consist of time domain reflectometry probes and tensiometers measured in-situ moisture content and pressure head, respectively. As surfactant solution was applied at the point source, a transient flow perturbation associated with the advance of the surfactant solution was observed. Above the top of the capillary fringe the advance of the surfactant solution caused a visible drainage front that radiated from the point source. Upon reaching the capillary fringe, the drainage front caused a localized depression of the capillary fringe below the point source because the air-entry pressure decreased in proportion to the decrease in surface tension caused by the surfactant. Eventually, a new capillary fringe height was established. The height of the depressed capillary fringe was proportional to height of the initial capillary fringe multiplied by the relative surface tension of the surfactant solution. The horizontal transport of surfactant in the depressed capillary fringe, driven primarily by the ambient groundwater flow, caused the propagation of a wedge-shaped drying front in the downgradient direction. Comparison of dye transport during the surfactant experiment to dye transport in an experiment without surfactant indicated that because surfactant-induced drainage decreased the storage capacity of the vadose zone, the dye breakthrough time to the water table was more than twice as fast when the contaminant solution contained surfactant. The extensive propagation of the drying front and the effect of vadose zone drainage on contaminant breakthrough time suggest the importance of considering surface tension effects on unsaturated flow and transport in systems containing surface-active organic contaminants or systems, where surfactants are used for remediation of the vadose zone or unconfined aquifers.     

Sorption of 1,2,4-trichlorobenzene and tetrachloroethene within an authigenic soil profile: Changes in Koc with soil depth

The sorption of 1,2,4-trichlorobenzene and tetrachloroethene was investigated in a series of well-controlled batch experiments, using authigenic soil materials from a profile extending to 2.5 m below ground surface. Batch experiment techniques were verified by study with both pulverized and unpulverized soil at different times of equilibration, using two widely different soil:water ratios, and at a wide range of aqueous concentration. Sorption isotherms were approximately linear, with sorption distribution coefficients (K_d) found to decrease roughly 100-fold down the soil profile. K_d decreased with depth to an extent greater than could be predicted on the basis of the only 10-fold decrease in natural solid organic matter (SOM) content and despite significantly higher specific surface area in the lower horizons. All base-extractable SOM in these deeper soil horizons was operationally defined as fulvic acid (FA), although there was also a significant fraction that was not extracted by the standard base technique. The lower K_d of the deeper soil horizons is believed to reflect a complex combination of (1) lower SOM content; (2) a more hydrophilic form of SOM; and (3) a more intimate association of the SOM with the mineral fraction, affecting its accessibility, sorptivity, or both. For the deeper horizons, an increase in overall K_d by more than 4-fold was observed on solids treated by either base extraction or H₂O₂ treatment, demonstrating that sorption to remaining soil components could be dramatically increased by fractional SOM removal and/or chemical alteration of the soil. A simple regression model that divides SOM into only two types (shallow and deep SOM) provides a reasonably good explanation of sorption in all seven horizons and suggests an order-of-magnitude variability in K_oc among surface soil and deeper horizons.     

A multi-flowpath model for the interpretation of immiscible displacement experiments in heterogeneous soil columns

This work focuses on the phenomenon of the immiscible two-phase flow of water and oil in saturated heterogeneous soil columns. The goal is to develop a fast and reliable method for quantifying soil heterogeneities for incorporation into the relevant capillary pressure and relative permeability functions. Such data are commonly used as input data in simulators of contaminant transport in the subsurface. Rate-controlled drainage experiments are performed on undisturbed soil columns and the transient response of the axial distribution of water saturation is determined from electrical measurements. The transient responses of the axial distribution of water saturation and total pressure drop are fitted with the multi-flowpath model (MFPM) where the pore space is regarded as a system of parallel paths of different permeability. The MFPM enables us to quantify soil heterogeneity at two scales: the micro-scale parameters describe on average the effects of pore network heterogeneities on the two-phase flow pattern; the macro-scale parameters indicate the variability of permeability at the scale of interconnected pore networks. The capillary pressure curve is consistent with that measured with mercury intrusion porosimetry over the low pressure range. The oil relative permeability increases sharply at a very low oil saturation (< 10^− 3) and tends to a high end value. The water relative permeability decreases abruptly at a low oil saturation (~ 0.1), whereas the irreducible wetting phase saturation is quite high. The foregoing characteristics of the two-phase flow properties are associated with critical (preferential) flowpaths that comprise a very small percentage of the total pore volume, control the overall hydraulic conductivity, and are consistent with the very broad range of pore-length scales usually probed in soil porous matrix.     

高原地区铬渣污染场地污染特性研究

在我国高原地区某铬渣污染场地进行钻孔取样,分析场地工程地质特性,对场地铬的污染状况及空间分布特征进行研究。结果表明:场地地质结构较单一,地下水丰富,土质的渗透性强,渗透系数在1.78×10-3~0.243 cm/s之间;场地铬污染严重,总铬与六价铬的浓度最大值分别为22 485.6 mg/kg和7 495.2 mg/kg,地下水中六价铬的浓度最大值为107.2 mg/L;通过剖面铬浓度分析:铬在纵向上浓度分布受土壤质地的影响,均呈现表层4 m浓度较高,4 m以下浓度较低且变化较小的规律。由Kriging插值法绘的铬浓度分布等值线图可清晰看出场地表层土表现出向沟谷位置迁移趋势,地下水中残留的铬向地下水流场方向迁移。     

Unidirectional gas flow in soil porosity resulting from barometric pressure cycles

During numerical simulation of air flow in the vadose zone, it was noticed that a small sinusoidal pressure would cause a gradual one-way migration of the pore gas. This was found to be a physical phenomenon, not a numerical artifact of the finite element simulation. The one-way migration occurs because the atmospheric pressure, and hence the air density, is slightly greater when air is flowing into the ground than when air is flowing out of the ground. A simple analytic theory of the phenomenon is presented, together with analytic calculations using actual barometric pressure data. In soil of one Darcy permeability, the one-way migration is of the order of a few tenths of a meter per year for either plane flow from ground surface or for radial flow from an open borehole. The migration is sufficiently small that it will have no practical consequences in most circumstances; however, investigators who conduct detailed numerical modeling should recognize that this phenomenon is not a numerical artifact in an apparently linear system.     

Crude oil contaminated soil washing in air sparging assisted stirred tank reactor using biosurfactants

This study investigated the removal of crude oil from soil using air sparging assisted stirred tank reactors. Two surfactants (rhamnolipid and sodium dodecyl sulfate, SDS) were tested and the effects of different parameters (i.e. temperature, surfactant concentrations, washing time, volume/mass ratio) were investigated under varying washing modes namely, stirring only, air sparging only and the combination of stirring and air sparging. The results showed that SDS removed more than 80% crude oil from non-weathered soil samples, whilst rhamnolipid showed similar oil removal at the third and fourth levels of the parameters tested. The oil removal ability of the seawater prepared solutions were better than those of the distilled water solutions at the first and second levels of temperature and concentration of surfactant solutions. This approach of soil washing was noted to be effective in reducing the amount of oil in soil. Therefore we suggested that a field scale test be conducted to assess the efficiency of these surfactants.     

Effects of heterogeneities on capillary pressure-saturation-relative permeability relationships

In theories of multiphase flow through porous media, capillary pressure-saturation and relative permeability-saturation curves are assumed to be intrinsic properties of the medium. Moreover, relative permeability is assumed to be a scalar property. However, numerous theoretical and experimental works have shown that these basic assumptions may not be valid. For example, relative permeability is known to be affected by the flow velocity (or pressure gradient) at which the measurements are carried out. In this article, it is suggested that the nonuniqueness of capillary pressure-relative permeability-saturation relationships is due to the presence of microheterogeneities within a laboratory sample. In order to investigate this hypothesis, a large number of "numerical experiments" are carried out. A numerical multiphase flow model is used to simulate the procedures that are commonly used in the laboratory for the measurement of capillary pressure and relative permeability curves. The dimensions of the simulation domain are similar to those of a typical laboratory sample (a few centimeters in each direction). Various combinations of boundary conditions and soil heterogeneity are simulated and average capillary pressure, saturation, and relative permeability for the "soil sample" are obtained. It is found that the irreducible water saturation is a function of the capillary number; the smaller the capillary number, the larger the irreducible water saturation. Both drainage and imbibition capillary pressure curves are found to be strongly affected by heterogeneities and boundary conditions. Relative permeability is also found to be affected by the boundary conditions; this is especially true about the nonaqueous phase permeability. Our results reveal that there is much need for laboratory experiments aimed at investigating the interplay of boundary conditions and microheterogeneities and their effect on capillary pressure and relative permeability.     

地下水曝气理论模型研究进展

地下水曝气(Air Sparging,AS)是修复饱和土壤及地下水有机污染的有效技术.AS多相流动过程中气液流动以及污染物传质过程的模型研究是AS技术的关键因素,详细介绍了近年来AS系统的理论模型方法及研究进展,并对其效果进行评价.     

Quantitative imaging of contaminant distributions in heterogeneous porous media laboratory experiments

Intermediate-scale laboratory experiments on heterogeneous porous media have been increasingly used for the study of saturated and unsaturated ground water systems. While the ability to reproduce field-scale heterogeneity in these experiments has advanced, the use of visualization or image analysis methods to characterize the spatial distribution of solute concentrations has largely remained at the homogeneous media level. To advance these imaging techniques we developed a generic image analysis package that, for the first time, automatically segments regions in photographic images that require unique concentration calibration curves due to varying porous media properties or lighting nonuniformities. As a robust test, our image analysis package was applied to an intermediate-scale flow tank experiment characterized by a correlated random permeability field with unprecedented resolution. Twenty-five distinct classes of porous media were developed and binned to the synthetic permeability field, creating an experimental field of 3456 rectangular cells and thereby ensuring the emplaced field closely matched the statistics of the original continuous distribution. Concentration distributions were determined for an experimental tracer run and the corresponding dispersion parameters were calculated. The closeness of the experimental, image-processed longitudinal dispersivity (4.6 x 10(-2) m) to that obtained from the field statistics (9.1 x 10(-2) m) verifies our image analysis technique.