Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.     

Flux-based assessment at a manufacturing site contaminated with trichloroethylene

Groundwater and contaminant fluxes were measured, using the passive flux meter (PFM) technique, in wells along a longitudinal transect passing approximately through the centerline of a trichloroethylene (TCE) plume at a former manufacturing plant located in the Midwestern US. Two distinct zones of hydraulic conductivity were identified from the measured groundwater fluxes; a 6-m-thick upper zone ( approximately 7 m to 13 m below the ground surface or bgs) with a geometric mean Darcy flux (q(0)) of 2 cm/day, and a lower zone ( approximately 13 m to 16.5m bgs) with a q(0) approximately 15 cm/day; this important hydrogeologic feature significantly impacts any remediation technology used at the site. The flux-averaged TCE concentrations estimated from the PFM results compared well with existing groundwater monitoring data. It was estimated that at least 800 kg of TCE was present in the source zone. The TCE mass discharge across the source control plane (85 m x 38 m) was used to estimate the "source strength" ( approximately 365 g/day), while mass discharges across multiple down-gradient control planes were used to estimate the plume-averaged, TCE degradation rate constant (0.52 year(-1)). This is close to the rate estimated using the conventional centerline approach (0.78 year(-1)). The mass discharge approach provides a more robust and representative estimate than the centerline approach since the latter uses only data from wells along the plume centerline while the former uses all wells in the plume.     

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.     

Temporal evolution of DNAPL source and contaminant flux distribution: impacts of source mass depletion

We investigated, using model simulations, the changes occurring in the distribution of dense non-aqueous phase liquid (DNAPL) mass (Sn) within the source zone during depletion through dissolution, and the resulting changes in the contaminant flux distribution (J) at the source control plane (CP). Two numerical codes (ISCO3D and T2VOC) were used to simulate selected scenarios of DNAPL dissolution and transport in three-dimensional, heterogeneous, spatially correlated, random permeability fields with emplaced sources. Data from the model simulations were interpreted based on population statistics (mean, standard deviation, coefficient of variation) and spatial statistics (centroid, second moments, variograms). The mean and standard deviation of the Sn and J distributions decreased with source mass depletion by dissolution. The decrease in mean and standard deviation was proportional for the J distribution resulting in a constant coefficient of variation (CV), while for the Sn distribution, the mean decreased faster than the standard deviation. The spatial distributions exhibited similar behavior as the population distribution, i.e., the CP flux distribution was more stable (defined by temporally constant second moments and range of variograms) than the Sn distribution. These observations appeared to be independent of the heterogeneity of the permeability (k) field (variance of the log permeability field=1 and 2.45), correlation structure (positive vs. negative correlation between the k and Sn domains) and the DNAPL dissolution model (equilibrium vs. rate-limited), for the cases studied. Analysis of data from a flux monitoring field study (Hill Air Force Base, Utah) at a DNAPL source CP before and after source remediation also revealed temporal invariance of the contaminant flux distribution. These modeling and field observations suggest that the temporal evolution of the contaminant flux distribution can be estimated if the initial distribution is known. However, the findings are preliminary and broader implications to sampling strategies for remediation performance assessment need to be evaluated in additional modeling and experimental studies.     

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.     

Concentration field and turbulent fluxes during the mixing of two buoyant plumes

In this work an experimental study of mixing of two identical plumes, carried out in a turbulent neutral boundary layer generated in a wind tunnel, is presented. Measurements have been performed with fast flame ionisation detectors (FFIDs) and a two-component Laser-Doppler Anemometer system. Results allow the study of both the average and the fluctuating concentration field, including the turbulent vertical and longitudinal mass fluxes, in single plumes and during the interaction of two identical plumes. This information gives insight into the details of the mixing phase of the two plumes. Results of trajectories and additional rise (due to plume interactions) have been compared with previous measurements carried out in laminar cross-flows, showing similar behaviour. Concentration distributions in plume cross-sections in turbulent cross-flows differ from those measured in laminar cross-flows. Average vertical and longitudinal velocity measurements into the plume core show the strength of the shielding effect of the upwind plume and some details of interaction between the counter-rotating vortex pairs (CVPs). For large values of the alignment angle φ, between the line joining the stacks and the cross-flow, an average negative vertical velocity is measured in the middle of the plume even if its centre of mass is rising. This downward velocity is induced by the slow interaction of the CVPs and generates a vertical stretching of the plume and negative rise enhancement. Vertical turbulent fluxes change sign on the plume centreline and are of opposite sign with respect to the longitudinal turbulent fluxes. Results indicate a good linearity between vertical turbulent fluxes and concentration gradients, with different proportionality for the top and bottom parts of the plume (especially in the near field) indicating that dispersion could be described by a gradient-transfer model.     

Estimation of Methyl tert -Butyl Ether Plume Length Using the Domenico Analytical Model

Methyl tert -butyl ether (MTBE) plume is controlled by many factors, primarily by groundwater flow velocity, dispersion, natural attenuation. This study employed an analytical model introduced by Domemico (1987, J. Hydrol 91 , 49-58.) to describe the MTBE concentration distribution horizontal pattern and estimated the MTBE plume length. The model was applied to 90 leaking underground storage tank cases in Los Angeles, CA, U.S.A. The analytical model was calibrated with field data for each ease using a Microsoft Excel spreadsheet program. Methyl tert -butyl ether concentrations in one source monitoring well and one to two downgradient centerline monitoring wells were used for each case study. When the centerline well is not available, the closest off-centerline wells were projected to the centerline using an ellipse trigonometry method. The model parameter values for longitudinal dispersivity, groundwater velocity, and degradation rate constant were calibrated using the field data and then used to estimate the maximum distance between source well and the plume edge. This study demonstrates that the Domenico model can be applied to MTBE plume investigation when adequate field data are available. The correlation coefficients calculated based on the results of the 90 case studies indicate that MTBE plume length has a poor correlation with MTBE concentration at the source well, and a moderate negative correlation with the degradation rate constant ( m 0.65) and u / v ratio (0.64). Furthermore, MTBE plume length has a poor correlation with the longitudinal dispersivity ( m 0.4), hydraulic gradient ( m 0.1), and groundwater velocity (0.17).     

Development and evaluation of the PRIME plume rise and building downwash model

A new Gaussian dispersion model, the Plume Rise Model Enhancements (PRIME), has been developed for plume rise and building downwash. PRIME considers the position of the stack relative to the building, streamline deflection near the building, and vertical wind speed shear and velocity deficit effects on plume rise. Within the wake created by a sharp-edged, rectangular building, PRIME explicitly calculates fields of turbulence intensity, wind speed, and streamline slope, which gradually decay to ambient values downwind of the building. The plume trajectory within these modified fields is estimated using a numerical plume rise model. A probability density function and an eddy diffusivity scheme are used for dispersion in the wake. A cavity module calculates the fraction of plume mass captured by and recirculated within the near wake. The captured plume is re-emitted to the far wake as a volume source and added to the uncaptured primary plume contribution to obtain the far wake concentrations. The modeling procedures currently recommended by the U.S. Environmental Protection Agency (EPA), using SCREEN and the Industrial Source Complex model (ISC), do not include these features. PRIME also avoids the discontinuities resulting from the different downwash modules within the current models and the reported overpredictions during light-wind speed, stable conditions. PRIME is intended for use in regulatory models. It was evaluated using data from a power plant measurement program, a tracer field study for a combustion turbine, and several wind-tunnel studies. PRIME performed as well as or better than ISC/SCREEN for nearly all of the comparisons.     

Theoretical analysis of deviations from local equilibrium during sorbing solute transport through idealized stratified aquifers

This paper studies the spreading characteristics of reactive solute plumes in idealized stratified aquifers. The aquifer consists of two layers having different permeabilities with flow parallel to the stratification. The solute is assumed to adsorb onto the aquifer solids according to a first-order reversible kinetic rate law; the adsorption parameters are spatially uniform. We use the Aris moment method to examine analytically the time evolution of the lower-order spatial moments of the depth-averaged contaminant plume for an instantaneous input of mass. The results demonstrate that sorption kinetics cause the total dissolved mass and average velocity of the contaminant plume to decrease with increasing travel time. The plume variance is shown to depend upon three factors: intra-layer longitudinal dispersion, intra-layer kinetics, and vertical averaging. The results indicate that the relative importance of sorption kinetics diminishes as the permeability contrast between the layers increases. We present a simple criterion that can be used to assess the applicability of the local equilibrium assumption in idealized stratified systems.     

Development and Evaluation of the PRIME Plume Rise and Building Downwash Model

ABSTRACT

A new Gaussian dispersion model, the Plume Rise Model Enhancements (PRIME), has been developed for plume rise and building downwash. PRIME considers the position of the stack relative to the building, streamline deflection near the building, and vertical wind speed shear and velocity deficit effects on plume rise. Within the wake created by a sharp-edged, rectangular building, PRIME explicitly calculates fields of turbulence intensity, wind speed, and streamline slope, which gradually decay to ambient values downwind of the building. The plume trajectory within these modified fields is estimated using a numerical plume rise model. A probability density function and an eddy diffusivity scheme are used for dispersion in the wake. A cavity module calculates the fraction of plume mass captured by and recirculated within the near wake. The captured plume is re-emitted to the far wake as a volume source and added to the uncaptured primary plume contribution to obtain the far wake concentrations.

The modeling procedures currently recommended by the U.S. Environmental Protection Agency (EPA), using SCREEN and the Industrial Source Complex model (ISC), do not include these features. PRIME also avoids the discontinuities resulting from the different downwash modules within the current models and the reported overpredictions during light-wind speed, stable conditions. PRIME is intended for use in regulatory models. It was evaluated using data from a power plant measurement program, a tracer field study for a combustion turbine, and several wind-tunnel studies. PRIME performed as well as or better than ISC/SCREEN for nearly all of the comparisons.     

Characterization of preferential flow in undisturbed, structured soil columns using a vertical TDR probe

Rapid movement of agricultural chemicals through soil to groundwater via preferential flow pathways is one cause of water contamination. Previous studies have shown that time domain reflectometry (TDR) could be used to characterize solute transport in soil. However, previous studies have only scarcely addressed preferential flow. This study presents an extended application of TDR for determining preferential flow properties. A TDR method was tested in carefully controlled laboratory experiments using 20-cm long and 12-cm diameter undisturbed, structured soil columns. The method used a vertically installed TDR probe and a short pulse of tracer application to obtain residual mass (RM) breakthrough curves (BTC). The RM BTC obtained from TDR were used to estimate mobile/immobile model (MIM) parameters that were compared to the parameter estimates from effluent data. A conventional inverse curve fitting method (CXTFIT) was used to estimate parameters. The TDR-determined parameters were then used to generate calculated effluent BTC for comparison with observed effluent BTC for the same soil columns. Time moments of the calculated and observed BTC were calculated to quantitatively evaluate the calculated BTC. Overall, the RM BTC obtained from TDR were similar to the RM BTC obtained from effluent data. The TDR-determined parameters corresponded well to the parameters obtained from the effluent data, although they were not within the 95% confidence intervals. Correlation coefficients between the parameters obtained from TDR and from effluent data for the immobile water fraction (theta im/theta), mass exchange coefficient (alpha), and dispersion coefficient (Dm) were 0.95, 0.95, and 0.99, respectively. For three of the four soil cores, theta im/theta ranged from 0.42 to 0.82, indicating considerable preferential flow. The TDR-calculated effluent BTC also were similar to the observed effluent BTC having an average coefficient of determination of 0.94. Time moments obtained from calculated BTC were representative of those obtained from observed BTC. The vertical TDR probe method was simple and minimally destructive and provided representative preferential flow properties that enabled the characterization of solute transport in soil.     

Pseudo-source parameters for flares: Derivation,implementation, and comparison

The United States Environmental Protection Agency (US EPA) flare pseudo-source parameters are over 30 years old and few dispersion modellers understand their basis and underlying assumptions. The calculation of plume rise from the user inputs of pseudo-stack diameter, temperature and velocity have the most influence on air dispersion model predictions of ground-level concentrations. Regulatory jurisdictions across Canada, the United States and around the world have adopted their own approach to pseudo-source parameters for flares; all relate buoyancy flux to the heat release rate, none consider momentum flux and flare tip downwash as adopted by the Alberta Energy Regulator (AER). This paper derives the plume buoyancy flux for flares burning a gas in terms of combustion variables readily known or calculated without simplifying assumptions. Dispersion model prediction sensitivity to flared gas composition, temperature and velocity, and ambient conditions are now correctly handled by the AER approach. The AER flare pseudo-source parameters are based on both the buoyancy and momentum flux, thus conserving energy and momentum. The AER approach to calculate the effective source height for flares during varying wind speeds is compared to the US EPA approach. Instead of a constant source for all meteorological conditions, multiple co-located sources with varying effective stack height and diameter are used. AERMOD is run with the no stack tip downwash option as flare stack tip downwash is accounted for in the effective stack height rather than the AERMOD model calculating the downwash incorrectly using the pseudo-source parameters. The modelling approaches are compared for an example flare. Maximum ground level predictions change, generally increasing near the source and decreasing further away, with the AER flare pseudo-source parameters. It's time to update how we model flares.

Implications: What are the implications of continuing to model flare source parameters using the overly simplified US EPA approach? First, the regulators perpetuate the myths that the flare source height, temperature, diameter and velocity are constant for all wind speeds and ambient temperatures. Second, that it is acceptable to make simplifying assumptions that violate the conservation of momentum and energy principles for the sake of convenience. Finally, regulatory decisions based on simplified source modelling result in predictions that are not conservative (or realistic). The AER regulatory approach for flare source parameters overcomes all of these shortcomings. AERflare is a publicly available spreadsheet that provides the “correct” inputs to AERMOD.     

Quantification of mass fluxes and natural attenuation rates at an industrial site with a limited monitoring network: a case study

At many "real world" field sites, the number of available monitoring wells is limited due to economic or geological reasons. Under such restricted conditions, it is difficult to perform a reliable field investigation and to quantify primary lines of evidence for natural attenuation (NA), like the documentation of a decrease of contaminant mass flux in flow direction. This study reports the results of a groundwater investigation at a former manufactured gas plant situated in a Quaternary river valley in southwest Germany. The location, infrastructure and aquifer setting are typical of many industrial sites in Germany. Due to difficult drilling conditions (coarse glaciofluvial gravel deposits and an anthropogenic fill above the aquifer), only 12 monitoring wells were available for the investigation and localisation of the contaminant plume. These wells were situated along three control planes (CP) downgradient from the contaminant source, with four wells along each plane. Based on the sparse set of monitoring wells, field scale mass fluxes and first-order natural attenuation rate constants of benzene, toluene, ethylbenzene, and o-xylene and p-xylene (BTEX) and low molecular weight polycyclic aromatic hydrocarbons (PAH) were estimated utilizing different point scale and also a new integral investigation method. The results show that even at a heterogeneous site with a sparse monitoring network point scale investigation methods can provide reliable information on field scale natural attenuation rates, if a dependable flow model or tracer test data is available. If this information is not available, only the new integral investigation method presented can yield adequate results for the quantification of contaminant mass fluxes under sparse monitoring conditions.     

Monte Carlo simulation of nitrogen oxides dispersion from a vehicular exhaust plume and its sensitivity studies

The pollutant dispersion behavior from the vehicular exhaust plume has a direct impact on human health, particularly to the drivers, bicyclists, motorcyclists, pedestrians, people working nearby and vehicle passengers. A two-dimensional pollutant dispersion numerical model was developed based on the joint-scalar probability density function (PDF) approach coupled with a k–ε turbulence model to simulate the initial dispersion process of nitrogen oxides, temperature and flow velocity distributions from a vehicular exhaust plume. A Monte Carlo algorithm was used to solve the PDF transport equations in order to obtain the dispersion distribution of nitrogen oxides concentration. The model was then validated by a series of sensitivity experimental studies in order to assess the effects of vehicular exhaust tailpipe velocities, wind speeds and chemistry on the initial dispersion of NO and NO₂ mass concentrations from the vehicular exhaust plume. The results show that the mass concentrations of nitrogen oxides decrease along the centerline of the vehicular exhaust plume in the downstream distance. The dispersion process can be enhanced when the vehicular exhaust tailpipe velocity is much larger than the wind speed. The oxidation reaction of NO plays an important role when the wind speed is large and the vehicular exhaust exit velocity is small, which leads to chemical reduction of NO, and the formation and accumulation of NO₂ in the exhaust plume. It is also found that the effect of vehicular exhaust-induced turbulence in the vicinity of the exhaust tailpipe exit is more dominant than the effect of wind turbulence, while the wind turbulence gradually shows a significant role for the dispersion of nitrogen oxides along with the development of exhaust plume. The range of dispersion of nitrogen oxides in the radial direction is increased along with the development of vehicular exhaust plume.     

Influence of wall roughness on the dispersion of a passive scalar in a turbulent boundary layer

Many towns and cities consist of similarly sized buildings in relatively regular arrangements with smaller scale roughness elements such as roofs, chimneys and balconies. The objective of this study is to investigate how small scale roughness elements modify the influence of the large scale organized roughness on the dispersion of a passive scalar in a turbulent boundary layer. Wind tunnel experiments were performed using a passive tracer released from a line source and concentration profiles were measured with a Flame Ionisation Detector. The measurements are compared with numerical solutions of the advection–diffusion equation.The results show that decreasing the cavity aspect ratio increases the turbulent vertical mass fluxes, and that the small scale roughness enhances these fluxes, but only in the skimming flow regime. Numerical simulations showed that outside the roughness sub-layer (RSL) the changes in surface roughness could be accounted for by a simple variation of the friction velocity, but inside the RSL the spatial variability of the flow imposed by the roughness elements has much more influence. A simple model for a spatially averaged dispersion coefficient in the RSL has been developed and is shown to agree satisfactorily with the concentrations measured in these experiments.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Changes in contaminant mass discharge from DNAPL source mass depletion: evaluation at two field sites

Changes in contaminant fluxes resulting from aggressive remediation of dense nonaqueous phase liquid (DNAPL) source zone were investigated at two sites, one at Hill Air Force Base (AFB), Utah, and the other at Ft. Lewis Military Reservation, Washington. Passive Flux Meters (PFM) and a variation of the Integral Pumping Test (IPT) were used to measure fluxes in ten wells installed along a transect down-gradient of the trichloroethylene (TCE) source zone, and perpendicular to the mean groundwater flow direction. At both sites, groundwater and contaminant fluxes were measured before and after the source-zone treatment. The measured contaminant fluxes (J; ML(-2)T(-1)) were integrated across the well transect to estimate contaminant mass discharge (M(D); MT(-1)) from the source zone. Estimated M(D) before source treatment, based on both PFM and IPT methods, were approximately 76 g/day for TCE at the Hill AFB site; and approximately 640 g/day for TCE, and approximately 206 g/day for cis-dichloroethylene (DCE) at the Ft. Lewis site. TCE flux measurements made 1 year after source treatment at the Hill AFB site decreased to approximately 5 g/day. On the other hand, increased fluxes of DCE, a degradation byproduct of TCE, in tests subsequent to remediation at the Hill AFB site suggest enhanced microbial degradation after surfactant flooding. At the Ft. Lewis site, TCE mass discharge rates subsequent to remediation decreased to approximately 3 g/day for TCE and approximately 3 g/day for DCE approximately 1.8 years after remediation. At both field sites, PFM and IPT approaches provided comparable results for contaminant mass discharge rates, and show significant reductions (>90%) in TCE mass discharge as a result of DNAPL mass depletion from the source zone.     

Analysis of the long-term behavior of solute transport with nonlinear equilibrium sorption using breakthrough curves and temporal moments

We analyzed the long-term behavior of breakthrough curves (BTCs) and temporal moments of a solute subjected to Freundlich equilibrium sorption (s = kc(n)). For one-dimensional transport in a homogeneous porous medium, we derived a power-law relation between travel time, tau, and solute displacement, chi, with the exponent being equal to the Freundlich n exponent. The mean solute velocity, derived from the first time moment, was found to change as tau(n-1). For n values larger than 0.66, the second time moment could be related to c chi(2/n), where c is a constant. An approach based on the use of a critical concentration was developed to estimate the presence of the asymptotic regime in the tail of the BTC. This approach was tested successfully using numerical case studies. One-dimensional numerical simulations with varying values of k, n and initial mass were run to verify the closed form analytical expressions for the large time behavior of temporal moments and the tailing part of breakthrough curves. Good agreement between the slope of the tailing part of log-log transformed BTCs and the predicted slope using asymptotic theory was found. Asymptotic theory in general underestimated the magnitude of the concentration in the tail. The quality of the estimated concentrations in the tail improved for small values of the dispersivity. Experimental BTCs of uranin and benazolin were analyzed in combination with sorption/desorption batch experiments using asymptotic theory. A good agreement between the value of n parameter derived from desorption experiment with benazolin and the value of the n parameter derived from the tail of the BTC was found.     

A complex terrain dispersion model for regulatory applications

This paper demonstrates the development of a model designed to estimate concentrations associated with a source situated in complex terrain. The model is designed to provide estimates of concentration distributions and is thus primarily suitable for regulatory applications. The model assumes that the concentration at a receptor is a combination of concentrations caused by two asymptotic states: the plume remains horizontal, and the plume climbs over the hill. The factor that weights the two states is a function of the fractional mass of the plume above the dividing streamline height. The model has been evaluated against data from four complex terrain sites. The evaluation shows that the model performs at least as well as CTDMPLUS (Perry, S.G., 1992. CTDMPLUS, a dispersion model for sources near complex topography. Part I: technical formations. Journal of Applied Meteorology 31, 633–645), a more comprehensive model designed for complex terrain applications.     

Impact of transverse and longitudinal dispersion on first-order degradation rate constant estimation

A two-dimensional analytical model is employed for estimating the first-order degradation rate constant of hydrophobic organic compounds (HOCs) in contaminated groundwater under steady-state conditions. The model may utilize all aqueous concentration data collected downgradient of a source area, but does not require that any data be collected along the plume centerline. Using a least squares fit of the model to aqueous concentrations measured in monitoring wells, degradation rate constants were estimated at a former manufactured gas plant (FMGP) site in the Midwest U.S. The estimated degradation rate constants are 0.0014, 0.0034, 0.0031, 0.0019, and 0.0053 day(-1) for acenaphthene, naphthalene, benzene, ethylbenzene, and toluene, respectively. These estimated rate constants were as low as one-half those estimated with the one-dimensional (centerline) approach of Buscheck and Alcantar [Buscheck, T.E., Alcantar, C.M., 1995. Regression techniques and analytical solutions to demonstrate intrinsic bioremediation. In: Hinchee, R.E., Wilson, J.T., Downey, D.C. (Eds.), Intrinsic Bioremediation, Battelle Press, Columbus, OH, pp. 109-116] which does not account for transverse dispersivity. Varying the transverse and longitudinal dispersivity values over one order of magnitude for toluene data obtained from the FMGP site resulted in nearly a threefold variation in the estimated degradation rate constant-highlighting the importance of reliable estimates of the dispersion coefficients for obtaining reasonable estimates of the degradation rate constants. These results have significant implications for decision making and site management where overestimation of a degradation rate may result in remediation times and bioconversion factors that exceed expectations. For a complex source area or non-steady-state plume, a superposition of analytical models that incorporate longitudinal and transverse dispersion and time may be used at sites where the centerline method would not be applicable.