Assessing the impacts of partial mass depletion in DNAPL source zones I. Analytical modeling of source strength functions and plume response

Analytical solutions are developed for approximating the time-dependent contaminant discharge from DNAPL source zones undergoing dissolution and other decay processes. The source functions assume a power relationship between source mass and chemical discharge and can consider partial DNAPL source remediation (depletion) at any time after the initial DNAPL release. The source functions are used as a time-dependent boundary condition in an idealized chemical transport model to develop leading order approximations of the plume response to DNAPL source removal. The results suggest that partial DNAPL remediation does not tend to have a dramatic impact on the maximum extent of the plume if very low concentration values are used to define the plume boundaries. However, the solutions show that partial DNAPL removal from the source zone is likely to lead to large reductions in plume concentrations and mass, and it reduces the longevity of the plume. When the mass discharge from the source zone is linearly related to the DNAPL mass, it is shown that partial DNAPL depletion leads to linearly proportional reductions in the plume mass and concentrations.     

Monitoring groundwater contamination and delineating source zones at industrial sites: uncertainty analyses using integral pumping tests

Field-scale characterisations of contaminant plumes in groundwater, as well as source zone delineations, are associated with uncertainties that can be considerable. A major source of uncertainty in environmental datasets is due to variability of sampling results, as a direct consequence of the heterogeneity of environmental matrices. We develop a methodology for quantifying uncertainties in field-scale mass flow and average concentration estimations, using integral pumping tests (IPTs), where the contaminant concentration is measured as a function of time in a pumping well. This procedure increases the sampling volume and reduces the effect of small-scale variability that may bias point-scale measurements. In particular, using IPTs, the interpolation uncertainty of conventional point-scale measurements is transformed to a quantifiable uncertainty related to the (unknown) plume position relative to the pumping well. We show that this plume position uncertainty generally influenced the predicted mass flows and average concentrations (of acenapthene, benzene and CHCs) to a greater extent than a boundary condition uncertainty related to the local water balance, considering 19 control planes at a highly heterogeneous industrial site in southwest Germany. Furthermore, large (order of magnitude) uncertainties only occurred if the conditions were strongly heterogeneous in the nearest vicinity of the well. We also develop a consistent methodology for an assessment of the combined effect of uncertainty in hydraulic conditions and uncertainty in reactive transport parameters for delimiting of both contaminant source zones and zones absent of source, based on (downgradient) IPTs.     

Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.     

Refinement of the density-modified displacement method for efficient treatment of tetrachloroethene source zones

A novel method to remediate dense nonaqueous phase liquid (DNAPL) source zones that incorporates in situ density conversion of DNAPL via alcohol partitioning followed by displacement with a low interfacial tension (IFT) surfactant flood has been developed. Previous studies demonstrated the ability of the density-modified displacement (DMD) method to recover chlorobenzene (CB) and trichloroethene (TCE) from heterogeneous porous media without downward migration of the dissolved plume or free product. However, the extent of alcohol (n-butanol) partitioning required for in situ density conversion of high-density NAPLs, such as tetrachloroethene (PCE), could limit the utility of the DMD method. Hence, the objective of this study was to compare the efficacy of two n-butanol delivery approaches: an aqueous solution of 6% (wt) n-butanol and a surfactant-stabilized macroemulsion containing 15% (vol) n-butanol in water, to achieve density reduction of PCE-NAPL in two-dimensional (2-D) aquifer cells. Results of liquid-liquid equilibrium studies indicated that density conversion of PCE relative to water occurred at an n-butanol mole fraction of 0.56, equivalent to approximately 5 ml n-butanol per 1 ml of PCE when in equilibrium with an aqueous solution. In 2-D aquifer cell studies, density conversion of PCE was realized using both n-butanol preflood solutions, with effluent NAPL samples exhibiting density reductions ranging from 0.51 to 0.70 g/ml. Although the overall PCE mass recoveries were similar (91% and 93%) regardless of the n-butanol delivery method, the surfactant-stabilized macroemulsion preflood removed approximately 50% of the PCE mass. In addition, only 1.2 pore volumes of the macroemulsion solution were required to achieve in situ density conversion of PCE, compared to 6.4 pore volumes of the 6% (wt) n-butanol solution. These findings demonstrate that use of the DMD method with a surfactant-stabilized macroemulsion containing n-butanol holds promise as an effective source zone remediation technology, allowing for efficient recovery of PCE-DNAPL while mitigating downward migration of the dissolved plume and free product.     

Relative velocities of DNAPL and aqueous phase plume migration

Numerical simulation is used to examine the relative velocities of DNAPL and aqueous phase plumes in sandy aquifers where lateral spreading of DNAPL has occurred at the base of the aquifer. The scenario being modeled is one where a permeable aquifer is underlain by a sloping aquitard, which results in lateral migration of the DNAPL down the slope, in addition to lateral migration of an aqueous phase plume subject to a specified hydraulic gradient. A sensitivity analysis is presented to the impacts of both DNAPL properties and geologic properties. The most important chemical properties governing the relative velocities of the DNAPL and the shallow aqueous phase plume are the DNAPL viscosity and the aqueous component soil-water partition coefficient (Kd). The dip of the underlying aquitard was found to be relatively unimportant, at least for the range of values studied. The scenario under consideration can be important in conceptual model development and remedial design, as in certain cases DNAPL could be migrating in areas without the evidence of a well-developed aqueous phase plume. The implication of this work is that the absence of a shallow aqueous phase plume directly downgradient of a DNAPL source zone does not rule out the possibility of deep occurrences of DNAPL beyond the shallow monitoring well network. A further finding of this study is that the occurrence of a highly sorbing compound in groundwater at virtually any concentration may indicate the immediate upgradient presence of residual or pooled DNAPL.     

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.     

Assessing impacts of partial mass depletion in DNAPL source zones: II. Coupling source strength functions to plume evolution

Analytical solutions, describing the time-dependent DNAPL source-zone mass and contaminant discharge rate, derived previously in Part I [Falta, R.W., Rao, P.S., Basu, N., this issue. Assessing the impacts of partial mass depletion in DNAPL source zones: I. Analytical modeling of source strength functions and plume response. J. Contam. Hydrol.] are used as a flux-boundary condition in a semi-analytical contaminant transport model. These analytical solutions assume a power relationship between the flow-averaged source concentration, and the source DNAPL mass; the empirical exponent (gamma) is a function of the flow field heterogeneity, DNAPL architecture, and the correlation between them. The DNAPL source strength terms can account for partial source remediation, either at time zero, or at some later time after the DNAPL release. The transport model considers advection, retardation, three-dimensional dispersion, and sequential first-order decay/production of several species. A separate solution is used to compute the time-dependent mass of each contaminant in the plume. A series of examples using different values of gamma shows how the benefits of partial DNAPL source remediation can vary with site conditions. In general, when gamma>1, relatively large short-term reductions in the plume concentrations and mass occur, but the source longevity is not strongly affected. Conversely, when gamma<1, the short-term reductions in the plume concentrations and mass are smaller, but the source longevity can be greatly reduced. In either case, the source remediation effort is much more effective if it is undertaken at an early time, before much contaminant mass has entered the plume. If the remediation effort is significantly delayed, the leading parts of the plume are not affected by the source remediation, and additional control or remediation of the plume itself is required.     

Uncertainty in Nonpoint Source Pollution Models and Associated Risks

The usefulness of water quality simulation models for environmental management is explored with a focus on prediction uncertainty. The specific objective is to demonstrate how the usability of a flow and transport model (here: MACRO) can be enhanced by developing and analyzing its output probability distributions based on input variability. This infiltration-based model was designed to investigate preferential flow effects on pollutant transport. A statistical sensitivity analysis is used to identify the most uncertain input parameters based on model outputs. Probability distribution functions of input variables were determined based on field-measured data obtained under alternative tillage treatments. Uncertainty of model outputs is investigated using a Latin hypercube sampling scheme (LHS) with restricted pairing for model input sampling. Probability density functions (pdfs) are constructed for water flow rate, atrazine leaching rate, total accumulated leaching, and atrazine concentration in percolation water. Results indicate that consideration of input parameter uncertainty produces a 20% higher mean flow rate along with two to three times larger atrazine leaching rate, accumulated leachate, and concentration than that obtained using mean input parameters. Uncertainty in predicted flow rate is small but that in solute transport is an order of magnitude larger than that of corresponding input parameters. Macropore flow is observed to contribute to the variability of atrazine transport results. Overall, the analysis provides a quantification of prediction uncertainty that is found to enhance a user's ability to assess risk levels associated with model predictions.     

Dissolved plume attenuation with DNAPL source remediation, aqueous decay and volatilization--analytical solution, model calibration and prediction uncertainty

A vertically-integrated analytical model for dissolved phase transport is described that considers a time-dependent DNAPL source based on the upscaled dissolution kinetics model of Parker and Park with extensions to consider time-dependent source zone biodecay, partial source mass reduction, and remediation-enhanced source dissolution kinetics. The model also considers spatial variability in aqueous plume decay, which is treated as the sum of aqueous biodecay and volatilization due to diffusive transport and barometric pumping through the unsaturated zone. The model is implemented in Excel/VBA coupled with (1) an inverse solution that utilizes prior information on model parameters and their uncertainty to condition the solution, and (2) an error analysis module that computes parameter covariances and total prediction uncertainty due to regression error and parameter uncertainty. A hypothetical case study is presented to evaluate the feasibility of calibrating the model from limited noisy field data. The results indicate that prediction uncertainty increases significantly over time following calibration, primarily due to propagation of parameter uncertainty. However, differences between the predicted performance of source zone partial mass reduction and the known true performance were reasonably small. Furthermore, a clear difference is observed between the predicted performance for the remedial action scenario versus that for a no-action scenario, which is consistent with the true system behavior. The results suggest that the model formulation can be effectively utilized to assess monitored natural attenuation and source remediation options if careful attention is given to model calibration and prediction uncertainty issues.     

Uncertainty in Nonpoint Source Pollution Models and Associated Risks

The usefulness of water quality simulation models for environmental management is explored with a focus on prediction uncertainty. The specific objective is to demonstrate how the usability of a flow and transport model (here: MACRO) can be enhanced by developing and analyzing its output probability distributions based on input variability. This infiltration-based model was designed to investigate preferential flow effects on pollutant transport. A statistical sensitivity analysis is used to identify the most uncertain input parameters based on model outputs. Probability distribution functions of input variables were determined based on field-measured data obtained under alternative tillage treatments. Uncertainty of model outputs is investigated using a Latin hypercube sampling scheme (LHS) with restricted pairing for model input sampling. Probability density functions (pdfs) are constructed for water flow rate, atrazine leaching rate, total accumulated leaching, and atrazine concentration in percolation water. Results indicate that consideration of input parameter uncertainty produces a 20% higher mean flow rate along with two to three times larger atrazine leaching rate, accumulated leachate, and concentration than that obtained using mean input parameters. Uncertainty in predicted flow rate is small but that in solute transport is an order of magnitude larger than that of corresponding input parameters. Macropore flow is observed to contribute to the variability of atrazine transport results. Overall, the analysis provides a quantification of prediction uncertainty that is found to enhance a user's ability to assess risk levels associated with model predictions.     

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.     

Fate and contaminant transport model-driven probabilistic human health risk assessment of DNAPL-contaminated site

In this study, fate and contaminant transport model-driven human health risk indexes were calculated due to the presence of dense non-aqueous phase liquids (DNAPLs) in the subsurface environment of air force base area in Florida, USA. Source concentration data of DNAPLs was used for the calculation of transport model-driven health risk indexes for the children and adult sub-population via direct oral ingestion and skin dermal contact exposure scenario using 10,000 Monte Carlo type simulations. The highest variation in the probability distribution of transformed DNAPL compound (cis-dichloroethene (cis-DCE) > vinyl chloride (VC)) was observed as compared to parent DNAPL (tetrachloroethene (PCE)) based on the 50-year simulation timespan. Transformed DNAPL compounds (VC, cis-DCE) posed the highest risk to human health for a longer duration (up to 15 years) in comparison to parent DNAPL (PCE), as non-carcinogenic hazard quotient varied from 400 to 1100. Carcinogenic health risks were observed as 3-order of magnitude higher than safe limit (HQ_Safe < 10⁻⁶) from 2nd to 5th year timespan and fall in the high-risk zone, indicating the need for a remediation plan for a contaminated site. Variance attribution analysis revealed that concentration, body weight, and exposure duration (contribution percentage – 70 to 95%) were the most important parameters, highlighting the impact of dispersivity and exposure model in the estimation of risk indexes. This approach can help decision-makers when a contaminated site with partial data on hydrogeological properties and with higher uncertainty in model parameters is to be assessed for the formulation of remediation measures.

     

Uncertainty assessment of contaminant plume length estimates in heterogeneous aquifers

The Virtual Aquifer approach is used in this study to assess the uncertainty involved in the estimation of contaminant plume lengths in heterogeneous aquifers. Contaminant plumes in heterogeneous two-dimensional conductivity fields and subject to first order and Michaelis-Menten (MM) degradation kinetics are investigated by the center line method. First order degradation rates and plume lengths are estimated from point information obtained along the plume center line. Results from a Monte-Carlo investigation show that the estimated rate constant is highly uncertain and biased towards overly high values. Uncertainty and bias amplify with increasing heterogeneity up to maximum values of one order of magnitude. Calculated plume lengths reflect this uncertainty and bias. On average, plume lengths are estimated to about 50% of the true plume length. When plumes subject to MM degradation kinetics are investigated by using a first order rate law, an additional error is introduced and uncertainty as well as bias increase, causing plume length estimates to be less than 40% of the true length. For plumes with MM degradation kinetics, therefore, a regression approach is used which allows the determination of the MM parameters from center line data. Rate parameters are overestimated by a factor of two on average, while plume length estimates are about 80% of the true length. Plume lengths calculated using the MM parameters are thus closer to the correct length, as compared to the first order approximation. This approach is therefore recommended if field data collected along the center line of a plume give evidence of MM kinetics.     

Uncertainty analysis of parameters for modeling the transfer and fate of benzo(a)pyrene in Tianjin wastewater irrigated areas

A Monte Carlo simulation for uncertainty analysis of three key parameters (local coal consumption rate Q(1L), dry deposition velocity of aerosol particulate Kp and biodegradation rate of benzo(a)pyrene in soil and sediment K(R3)) was conducted in this study. Results of the simulation indicate that the three parameters were influenced by uncertainty and that all equilibrium concentrations in the four bulk compartments and various sub-compartments were log-normally distributed. However, the results also indicated that among the six primary transfer fluxes, erosion associated with solids in soil and deposition associated with solids in water, along with output from sewers were also log-normally distributed, while deposition from air to soil and biodegradation in soil and sediment followed normal distributions. The effect of uncertainty on the model results of the three key parameters was derived using a comparison of upper and lower of confidence interval boundaries at the 95% level of confidence. The results reveal that uncertainty in the key parameters had a more significant influence on equilibrium concentrations of the chemical in the bulk compartments of soil and sediment than on concentrations in the other two bulk compartments, various sub-compartments and the six predominant transfer fluxes.     

Mass removal of chlorinated ethenes from rough-walled fractures using permanganate

In situ chemical oxidation (ISCO) employing permanganate is an emerging technology that has been successful at enhancing mass removal from DNAPL source zones in unconsolidated media at the pilot-scale. The focus of this study was to evaluate the applicability of flushing a permanganate solution across two single vertical fractures in a laboratory environment to remove free phase DNAPL. The fracture experiments were designed to represent a portion of a larger fractured aquifer system impacted by a near-surface DNAPL spill over a shallow fractured rock aquifer. Each fracture was characterized by hydraulic and tracer tests, and the aperture field for one of the fractures was mapped using a co-ordinate measurement machine. Following DNAPL emplacement, a series of water and permanganate flushes were performed. To support observations from the fracture experiments, a set of batch experiments was conducted. The data from both fracture experiments showed that the post-oxidation effluent concentration was not impacted by the oxidant flush; however, changes in the aperture distribution, flow field, and flow rate were observed. These changes resulted in a significant decrease to the mass loading from the fractures, and were attributed to the build-up of oxidation by-products (manganese oxides and carbon dioxide) within the fracture which was corroborated by the batch experiment data and visual examination of the walls of one fracture. These results provide insight into the potential impact that a permanganate solution and oxidation by-products can have on the aperture distribution within a fracture and on DNAPL mass transfer rates. A permanganate flush or injection completed within a fractured rock aquifer may lead to the development of an insoluble product adjacent to the DNAPL which results in the reduction or complete elimination of advective regions near the DNAPL and reduces mass transfer rates. This outcome would have significant implications on the plume generating potential of the remaining DNAPL.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.     

Uncertainty analysis on simple mass balance model to calculate critical loads for soil acidity

Simple mass balance equations (SMBE) of critical acid loads (CAL) in forest soil were developed to assess potential risks of air pollutants to ecosystems. However, to apply SMBE reliably at large scales, SMBE must be tested for adequacy and uncertainty. Our goal was to provide a detailed analysis of uncertainty in SMBE so that sound strategies for scaling up CAL estimates to the national scale could be developed. Specifically, we wanted to quantify CAL uncertainty under natural variability in 17 model parameters, and determine their relative contributions in predicting CAL. Results indicated that uncertainty in CAL came primarily from components of base cation weathering (BC(w); 49%) and acid neutralizing capacity (46%), whereas the most critical parameters were BC(w) base rate (62%), soil depth (20%), and soil temperature (11%). Thus, improvements in estimates of these factors are crucial to reducing uncertainty and successfully scaling up SMBE for national assessments of CAL.     

Simultaneous optimization of dense non-aqueous phase liquid (DNAPL) source and contaminant plume remediation

A framework is developed for simultaneous, optimal design of groundwater contaminant source removal and plume remediation strategies. The framework allows for varying degrees of effort and cost to be dedicated to source removal versus plume remediation. We have accounted for the presence of physical heterogeneity in the DNAPL source, since source heterogeneity controls mass release into the plume and the efficiency of source removal efforts. We considered high and low estimates of capital and operating costs for chemical flushing removal of the source, since these are expected to vary form site to site. Using the lower chemical flushing cost estimates, it is found that the optimal allocation of funds to source removal or plume remediation is sensitive to the degree of heterogeneity in the source. When the time elapsed between the source release and the implementation of remediation was varied, it was found that, except for the longest elapsed time (50,000 days), a combination of partial source removal and plume remediation was most efficient. When first-order, dissolved contaminant degradation was allowed, source removal was found to be unnecessary for the cases where the degradation rate exceeded intermediate values of the first-order rate constant. Finally, it was found that source removal became more necessary as the degree of aquifer heterogeneity increased.     

Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid

Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.     

A sensitivity analysis of adsorption and degradation parameters in the modeling of pesticide transport in soils

The increasing use of deterministic models in predicting the movement of pesticides in soils, has focused attention on the evaluation of major parameters which represent attenuation factors of organics in the subsurface. These parameters are the degradation rate constant and the adsorption constant for the pesticide. In view of the large in situ variability of these parameters and of the difficulty in obtaining accurate field data, there is a high degree of uncertainty associated with the results obtained from deterministic models. A sensitivity analysis is performed here to quantify the impact of such variation in each of these input parameters on the output results of an unsaturated zone transport model (PRZM). Results show that variations in these parameters about their respective mean values greatly affect the predicted concentration distributions, obtained after three years, of the pesticide aldicarb in all the soil profile. A 15–22% variation in the degradation constant, or a 24% variation in the adsorption constant, lead to a 100% uncertainty in the various simulation results defined as the cumulative quantity of aldicarb or the dissolved aldicarb concentration leached below the root zone (or the unsaturated zone) of the soil. Such a deterministic model presents a high degree of sensitivity to these input parameters. Accurate field data are then needed to obtain reliable model results in predicting pesticide movement inthe unsaturated zone.