Borden Aquifer Research Articles

Geostatistics of the Borden Aquifer: High‐Resolution Characterization Using Direct Groundwater Velocity Measurements

AbstractIn 1986, a seminal data set from the Canadian Forces Base (C.F.B.) Borden aquifer, Ontario, Canada, was published, illustrating, in unprecedented detail, the spatial distribution of hydraulic conductivity (K). Among many contributions attached to that data set was a geostatistical examination of field‐based data for comparison with theoretical predictions of macro‐dispersivity. However,that work treatedKas a static parameter and the sole source of flow variability. Here, point velocity probes (PVPs) are used to extend the earlier work by collecting a novel high‐resolution data set of groundwater velocity (v) measurements in the C.F.B. Borden aquifer. Velocity is a dynamic parameter of fundamental importance, closely tied to solute dispersion. Over 400 velocity measurements were collected along a transect perpendicular to flow, analyzed geostatistically, and compared with the analysis of the B‐B′ cross‐section ofKreported by Sudicky (1986),https://doi.org/10.1029/wr022i013p02069. The PVP measurements exhibited geostatistics similar to those previously estimated by Sudicky (1986),https://doi.org/10.1029/wr022i013p02069. This finding suggests, as implicitly assumed in the previous work, the distribution ofvis primarily controlled byK. PVPs also provided a novel, high‐resolution data set of groundwater flow directions. Since the ultimate objective of aquifer characterization includes the definition of velocity fields, this work not only extends the 1986 work, but also demonstrates a viable alternative for characterizing flow patterns in aquifers—with the advantage thatdirect vmeasurements reflect variability in porosity and hydraulic gradient, as well asK. This could ultimately be advantageous at sites with greater heterogeneity or other dynamic hydrogeological variabilities more pronounced than those at the Borden site.

Stochastic seepage and slope stability analysis using vine-copula based multivariate random field approach: Consideration to non-Gaussian spatial and cross-dependence structure of hydraulic parameters

Stochastic seepage and slope stability analysis is conventionally performed in a random field framework. However, most of the studies are limited to Gaussian spatial and cross-dependence structure of hydraulic parameters. Using a well documented hydraulic conductivity (k) data from Borden aquifer, Canada (Sudicky, 1986), evidence of non-Gaussian spatial dependence is provided within a copula framework. It is shown that the non-Gaussian spatial dependence structure is a field reality for k. To handle the non-Gaussian spatial as well as cross-dependence structure, a multivariate random field framework based on vine copula theory is presented. It is shown that the vine-copula approach can efficiently model the non-Gaussian dependence structure of hydraulic parameters. For investigating the practical engineering importance of dependence structure, stochastic seepage and slope stability analysis under steady and transient seepage conditions is conducted. It is shown that the assumption of arbitrary spatial dependence structure, can significantly affect (by a factor of 100) the failure probability of slopes across the entire acceptable range (Salgado and Kim, 2014) of 10-4 to 10-2. It is also shown that the choice of spatial dependence structure is more crucial than the cross-dependence for stochastic seepage and slope stability analysis.

Dilution enhancement in hierarchical and multiscale heterogeneous sediments

We quantify the dilution of solute clouds in geological formations displaying hierarchical and multiscale sedimentary architecture through the use of a Lagrangian framework. This allows for a fundamental understanding of how dilution arises from the hierarchical architecture of sedimentary facies, and enables for a quantitative decomposition of dilution into facies-related contributions at different scales within the hierarchy. The new developed semi-analytical solution that quantify the dilution index is based on hierarchical expressions of the spatial covariance of the log-conductivity. The spatial correlation structure in the covariance expression is defined by the probability of transitioning within and across facies types of different scales, which are parameterized by independent and physically quantifiable attributes of sediments (including geostatistical properties of the conductivity field) and the proportions and lengths of facies types. We illustrate the applicability of the model in the well-documented tracer test at the Borden research site (Canada). We show how different scales of sedimentary architecture contribute to the dilution enhancement of the solute cloud at Borden aquifer. By quantitatively decomposing the dilution index into facies-related contributions, we gain fundamental insights on the key factors controlling the time-dependent rate of dilution. The results also illustrate that the probability of transitioning from one facies to another (i.e. cross-transitions) at different scales defines the temporal scaling for enhanced dilution. Additionally, we perform sensitivity analyses to investigate the effects of mean difference in conductivity, volume proportion, the statistical anisotropy ratio, and the scale of heterogeneity on the overall solute dilution.

Sensing Coated Iron-Oxide Nanoparticles with Spectral Induced Polarization (SIP): Experiments in Natural Sand Packed Flow-Through Columns.

The development of nanoparticle-based soil remediation techniques is hindered by the lack of accurate in situ nanoparticle (NP) monitoring and characterization methods. Spectral induced polarization (SIP), a noninvasive geophysical technique, offers a promising approach to detect and quantify NPs in porous media. However, its successful implementation as a monitoring tool requires an understanding of the polarization mechanisms, the governing NP-associated SIP responses and their dependence on the stabilizing coatings that are typically used for NPs deployed in environmental applications. Herein, we present SIP responses (0.1-10 000 Hz) measured during injection of a poloxamer-coated superparamagnetic iron-oxide nanoparticle (SPION) suspension in flow-through columns packed with natural sand from the Borden aquifer. An advective-dispersive transport model is fitted to outflow SPION concentration measurements to compute average concentrations over the SIP spatial response domain (within the columns). The average SPION concentrations are compared with the real and imaginary components of the complex conductivity. Excellent correspondence is found between the average SPION concentrations inthe columns and the imaginary conductivity values, suggesting that NP-mediated polarization (that is, charge storage) increases proportionally with increasing SPION concentration. Our results support the possibility of SIP monitoring of spatial and temporal NP distributions, which can be immediately deployed in bench-scale studies with the prospect of future real-world field applications.

Contaminant tailing in highly heterogeneous porous formations: Sensitivity on model selection and material properties

Summary Coupled impacts of slow advection, diffusion and sorption were investigated using two heterogeneity models that differ in structure and in the mathematical framework that was used to simulate flow and transport and to quantify contaminant tailing. Both models were built using data from a highly heterogeneous exposure of the Borden Aquifer at a site located 2 km north-west of the Stanford–Waterloo experimental site at Canadian Forces Base Borden, Ontario, Canada. The inclusions-based model used a simplified representation of the different materials found at the site, while the second model was based on transitional probability geostatistics of the formation. These two models were used to investigate sensitivity of contaminant tailing on model selection and on geometric and material properties. While simulations were based on data collected at Borden, models were exercised beyond the geometric and material properties that characterize the site. Various realizations have identified very low conductive silty clay, found at volume fraction of 23.4%, as the material with dominant influence on tailing, and vertical diffusion in and out of low conductive units, affected by sorption, as the dominant transport mechanism causing tailing. The two models yielded almost identical transport results when vertical correlation lengths of silty clay were matched. Several practical implications relevant for characterization of low conductive units were identified and briefly discussed.

Characterization and quantification of aquifer heterogeneity using outcrop analogs at the Canadian Forces Base Borden, Ontario, Canada

Accurate characterization of internal structures and geometries of aquifers is critical for evaluation of plume migration and dispersion of contaminants. For this reason, high-resolution transport study field sites, such as the Waterloo Groundwater Research Site at the Canadian Forces Base Borden, Ontario, Canada, have been established. However, geological characterization at this site is based primarily on cores and shallow geophysical data. Outcrop analog studies offer detailed horizontal data that can help to build quantified models of aquifer heterogeneity. We used a combination of ground-based light detection and ranging (LiDAR) and high-resolution photographs at a sand quarry cut into Borden aquifer sediment to evaluate and quantify the distribution of lithofacies and hydrofacies that control flow properties in the Borden aquifer. We exposed sixteen ∼20 m × 1.5 m outcrops, LiDAR surveyed, photographed, and field mapped lithofacies at each exposure, and segmented the lithofacies from photographs to produce maps of facies distributions. We grouped different lithofacies into hydrofacies based on overall facies geometry and estimated hydraulic properties. We used LiDAR scans and the segmented facies maps to produce a digital outcrop model (DOM) of the site. The resultant DOM combines lithofacies and hydrofacies derived from field observations with high-resolution (5 mm) LiDAR data to reconstruct hydrofacies distributions in a three-dimensional (3-D) geomodel. The DOM offers a relatively complete horizontal correlation structure that was used in transition probability geostatistical modeling to create realizations of hydrofacies distributions in the aquifer at the study site.

Hydrophobic organic contaminant transport property heterogeneity in the Borden Aquifer

AbstractWe determined that the spatial heterogeneity in aquifer properties governing the reactive transport of volatile organic contaminants is defined by the arrangement of lithofacies. We measured permeability (k) and perchloroethene sorption distribution coefficient (Kd) for lithofacies that we delineated for samples from the Canadian Forces Base Borden Aquifer. We compiled existing data and collected 57 new cores to characterize a 30 m section of the aquifer near the test location of Mackay et al. (1986). The k and Kd were measured for samples taken at six elevations from all cores to create a data set consisting of nearly 400 colocated measurements. Through analysis of variance (corrected for multiple comparisons), we determined that the 12 originally mapped lithofacies could be grouped into five relatively distinct chemohydrofacies that capture the variability of both transport properties. The mean of ln k by lithofacies was related to the grain size and the variance was relatively consistent. In contrast, both the mean and variance of ln Kd were greater for more poorly sorted lithofacies, which were also typically more coarse‐grained. Half of the aquifer sorption capacity occurred in the three highest‐sorbing lithofacies but comprised only 20% of its volume. The model of the aquifer that emerged is that of discontinuous scour‐fill deposits of medium sand, generally characterized by greater Kd and k, within laterally extensive fine‐grained to very fine‐grained sands of lower Kd and k. Our findings demonstrate the importance of considering source rock composition, transport, and deposition processes when constructing conceptual models of chemohydrofacies.

On the importance of diffusion and compound-specific mixing for groundwater transport: An investigation from pore to field scale

Mixing processes significantly affect and limit contaminant transport and transformation rates in the subsurface. The correct quantification of mixing in groundwater systems must account for diffusion, local-scale dispersion and the flow variability in heterogeneous flow fields (e.g., flow-focusing in high-conductivity and de-focusing in low-conductivity zones). Recent results of multitracer laboratory experiments revealed the significant effect of compound-specific diffusive properties on the physical displacement of dissolved species across a representative range of groundwater flow velocities. The goal of this study is to investigate the role of diffusion and compound-specific mixing for solute transport across a range of scales including: (i) pore-scale (~10⁻² m), (ii) laboratory bench-scale (~10⁰ m) and (iii) field-scale (~10² m). We investigate both conservative and mixing-controlled reactive transport using pore-scale modeling, flow-through laboratory experiments and simulations, and field-scale numerical modeling of complex heterogeneous hydraulic conductivity fields with statistical properties similar to the ones reported for the extensively investigated Borden aquifer (Ontario, Canada) and Columbus aquifer (Mississippi, USA, also known as MADE site). We consider different steady-state and transient transport scenarios. For the conservative cases we use as a metric of mixing the exponential of the Shannon entropy to quantify solute dilution either in a given volume (dilution index) or in a given solute flux (flux-related dilution index). The decrease in the mass and the mass-flux of the contaminant plumes is evaluated to quantify reactive mixing. The results show that diffusive processes, occurring at the small-scale of a pore channel, strongly affect conservative and reactive solute transport at larger macroscopic scales. The outcomes of our study illustrate the need to consider and properly account for compound-specific diffusion and mixing limitations in order to accurately describe and predict conservative and reactive transport in porous media.

Simulating an exclusion zone for vapour intrusion of TCE from groundwater into indoor air

This paper is an extension of the work by Yu et al. (2009) to examine exposure pathways of volatile organic compounds (VOCs) originating from a NAPL source zone located below the water table, and their potential impact on multiple residential dwellings down-gradient of the source zone. The three-dimensional problem geometry is based on the Rivett (1995) field experiment in the Borden aquifer, and contains houses located both above and adjacent to the groundwater plume in order to define an exclusion zone. Simulation results using the numerical model CompFlow Bio indicate that houses which are laterally offset from the groundwater plume are less affected by vapour intrusion than those located directly above the plume due to limited transverse horizontal flux of TCE within the groundwater plume, in agreement with the ASTM (2008) guidance. Uncertainty in the simulated indoor air concentration is sensitive to heterogeneity in the permeability structure of a stratigraphically continuous aquifer, with uncertainty defined as the probability of simulated indoor air concentrations exceeding the NYSDOH (2005) regulatory limit. Within this uncertainty framework, this work shows that the Johnson and Ettinger (1991), ASTM (2008) and CompFlow Bio models all delineate an identical exclusion zone at a 99.9% confidence interval of indoor air concentrations based on the probability of exceedence.

Effects of non‐Gaussian copula‐based hydraulic conductivity fields on macrodispersion

This is an application of a spatial copula model that is fitted to a real world data set. The copula model allows modeling of pure spatial dependence independently of the marginal distribution. Using non‐Gaussian copula models it is demonstrated that the spatial dependence structure of the Borden aquifer is significantly non‐Gaussian—despite the fact that the Borden aquifer is commonly thought of as a relatively homogeneous porous medium with a small variance of hydraulic conductivity. In addition to evaluating the spatial dependence structure of the Borden hydraulic conductivity data set using copulas, goal of this study is to explore if the structure of the hydraulic conductivity field influences a physical property, such as plume evolution as evaluated by second spatial central moments of concentration fields. For this comparison, two types of hydraulic conductivity fields were fitted to the Borden hydraulic conductivity data set: one with a Gaussian and the other with a non‐Gaussian type of dependence. These two types of hydraulic conductivity fields were constructed such that their second‐order spatial moments are identical, and hence they cannot be distinguished by semivariogram‐based geostatistics. This paper illustrates that the spatial dependence structure of the Borden hydraulic conductivity data set is significantly non‐Gaussian. Despite the fact that Borden is a relatively homogeneous porous medium, and despite the fact that both types of spatial fields are not distinguishable by their variograms, the solute transport characteristics based on these two types of isotropic fields differ significantly in two‐dimensional settings. The difference is less pronounced in three‐dimensions with anisotropy. It is postulated that non‐Gaussian spatial dependence of hydraulic conductivity and a more skewed marginal distribution of hydraulic conductivity will have significant implications in the other more heterogeneous aquifers.

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC=0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC=0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.

Distribution of carbonaceous matter in lithofacies: Impacts on HOC sorption nonlinearity

Both the composition and distribution of the lithocomponents within an aquifer impact hydrophobic organic compound (HOC) transport. Using samples from the sandy, low fraction organic carbon content (foc~0.02%) Borden aquifer, we demonstrate how HOC sorption is controlled by the carbonaceous matter (CM) associated with calcareous sedimentary lithocomponents. Two-point isotherms using perchloroethene (PCE) as a sorbate showed that medium-grained lithofacies have a broader range of Kf (Freundlich coefficient), 1/n (Freundlich parameter) and foc than fine-grained facies. Dual-mode (linear+Freundlich) sorption modeling, fraction inorganic carbon (fic) and laboratory analyses confirm that both the magnitude and variability of PCE Kd (sorption distribution coefficient) in the Borden aquifer are controlled by the presence of heterogeneous CM in dark and very dark carbonate lithocomponents. Laboratory analyses and model results confirmed that the CM type controlling PCE sorption behavior in the Borden aquifer is in a condensed form, likely kerogen, contained within the carbonate matrix of the grains. The dark carbonate grains comprise a small proportion of the aquifer sediment (≪1%) and are found predominantly in medium-grained lithofacies in the Borden aquifer. These results show that increased heterogeneity, HOC mass storage and sorption nonlinearity associated with medium-grained lithofacies impact HOC transport in historically contaminated sedimentary aquifers.

Field GPR monitoring of biostimulation in saturated porous media

Abstract Time-lapse borehole radar was used to monitor a sandy aquifer with dielectric property changes hypothesized to result from biomass growth and biodegradation of hydrocarbons. A blend of gasoline and ethanol was released below the water table at Canadian Forces Base (CFB) Borden, Canada, and a source of oxygen was used for cyclic stimulation of microbial activity over a period of two years. A dense grid of fourteen borehole ground-penetrating radar (GPR) pairs monitoring the bioactive region showed 200 MHz radar wave velocity changes of ± 4 % and signal attenuation changes of ± 25 % during three cycles of variable biostimulation. GPR signal changes correlated spatially and temporally to independent measurements of groundwater velocity flow changes and geochemical variations that occurred in response to microbial activity. Greater relative changes in radar wave velocity of propagation were observed in the region of enhanced bacterial stimulation, adjacent to the oxygen release wells, and along the path of the hydrocarbon plume where biomass growth was the greatest. In the zone of maximum biological activity, radar wave velocity decreased during two cycles of enhanced biostimulation, whereas it increased during the intervening period of low-level biostimulation. Monitored regions at the fringe of the plume and farther down-gradient of the oxygen source, where biostimulation was less or absent, exhibited GPR signal changes of lesser magnitude and consistency. Spatial and temporal variabilities of GPR observations indicate a high degree of transient heterogeneity within the relatively homogeneous Borden aquifer as a result of hydrocarbon biodegradation. Mechanisms postulated to cause the dielectric property changes observed in the radar data are biogenic gas formation, mineral dissolution/precipitation, and direct biomass growth. Geochemical data, in-situ groundwater velocity measurements and biomass quantification suggest biomass formation in the pore space as a plausible mechanism for the changes observed in the aquifer. Therefore, at 200 MHz frequency, biomass formation is observed to cause a decrease of EM wave velocity of propagation suggesting an increase of the bulk dielectric constant of the water saturated medium. This finding is in agreement with published laboratory-scale GPR monitoring of microbial growth in porous media. This study shows that time-lapse GPR along with supporting biogeochemical observations can be used for monitoring of biological activity at the field scale.

Monitoring Lateral Transport of Ethanol and Dissolved Gasoline Compounds in the Capillary Fringe

Fuel mixtures composed of gasoline and ethanol are lighter than water and, if enough volume is released into the unsaturated zone, they accumulate in the capillary fringe, acting as a source for dissolved plumes. To evaluate different sampling techniques and transport in the capillary fringe, two controlled releases of gasoline and ethanol mixtures were conducted in the unsaturated zone at the CFB Borden aquifer. Lateral flow and transport in the capillary fringe is well documented, but this is the first field documentation of transport of organic compounds in the capillary fringe following fuel spills. Transport of both ethanol and hydrocarbon compounds in the capillary fringe was significant, ethanol being transported exclusively above the water table. Significant concentrations of benzene were found above the water table up to 6 m downgradient from the source. The groundwater sampling techniques evaluated were fully screened monitoring wells; multilevel wells constructed with ceramic porous cups located in both the capillary fringe and below the water table; and soil coring. The fully screened monitoring well was unable to draw water from the capillary fringe and so failed to adequately describe the contaminant distribution. Pore water concentrations obtained by sampling the multilevel porous cups and calculated based on analysis of soil core yielded similar results.

Characterization of a heterogeneous DNAPL source zone in the Borden aquifer using partitioning and interfacial tracers: Residual morphologies and background sorption

A partitioning interwell tracer test (PITT) was performed in the Borden sand aquifer to characterize an aged heterogeneous DNAPL source zone. This zone evolved during 5 years of natural groundwater flow following the infiltration of 50 L chlorinated solvents DNAPL. To assess the lateral variability of remaining DNAPL mass and morphology, four sweepzones were analyzed. The low saturation residual nature of the source zone required correction of tracer breakthrough data for natural background sorption. Corrected estimates of the DNAPL percentage remaining (total 13.2–16.6%), average saturation (0.05–0.18%) and distribution across the sweepzones were in good agreement with previous findings based on detailed transect monitoring, core analyses and ground-penetrating radar reflection. Using a newly defined metric “average spherical radius equivalent (ASRE)”, sweepzone estimates of the average size of DNAPL presence indicated the dominance of single pore DNAPL blobs and suggested the absence of DNAPL pools. Tracer tests indicated that DNAPL presence in the most DNAPL depleted sweepzone was potentially overestimated due to increased sediment sorption by residualized Sudan IV that was added to the DNAPL infiltrate. As hydrophobic compounds are normally present in spent solvent DNAPL, this suggests that additional sorption needs to be considered when using PITTs to characterize aged DNAPL source zones.

Effects of hydraulic conductivity heterogeneity on vadose zone response to pumping in an unconfined aquifer

Summary It is of great importance to be able to properly simulate flow mechanisms within the vadose zone as they are controlling factors for solute transport to groundwater bodies. The highly detailed pumping test data set collected by Bevan et al. (2005) at the Borden aquifer provides a unique opportunity to investigate the controlling factors for fluid flow and moisture distribution in the vadose zone in response to pumping. The field results show capillary fringe thicknesses that increased with duration of pumping, and decreased with distance from the well. This increased thickness was persistent for the duration of the 7 day test. Previous numerical analysis of the pumping test has been able to replicate the observed moisture contents at discrete time intervals ( Moench, 2008 ), but the physical mechanisms controlling the moisture content observations are poorly understood. Hydraulic conductivity heterogeneity has been proposed as a potential mechanism for the capillary fringe extension observed in the field. Using stochastic hydraulic conductivity fields, moisture content distributions observed during the Bevan et al. (2005) pumping test were simulated using a variably saturated numerical model. A Monte Carlo analysis was performed and ensemble results are presented. The ensemble mean hydraulic head drawdown was an adequate match to the field data, although there was a small but consistent over prediction of drawdown. The ensemble mean thickness of the capillary fringe was not significantly different from the result of a homogeneous simulation, and did not replicate the increasing thickness observed in the field. The ensemble mean capillary fringe extension was not found to be dependent upon distance from the pumping well or duration of pumping. Zones of perched water were formed in many of the heterogeneous realizations; however, neutron probe data collected during the field experiment does not support the presence of these perched zones.

Linking hierarchical stratal architecture to plume spreading in a Lagrangian‐based transport model: 2. Evaluation using new data from the Borden site

A new data set collected at the well‐documented Borden research site was used in order to evaluate a newly published but as yet untested idea for stochastic modeling (Ramanathan et al., 2008). The new data set reveals the stratal architecture of the Borden aquifer and allowed us to determine how the stratal architecture, at different scales, controlled the macrodispersion observed in the original natural gradient tracer test. The newly published idea for modeling uses a Lagrangian‐based model for the particle displacement variance developed from independent, physically based, quantifiable univariate statistics, including the proportions and mean length of the strata. The method for defining model parameters avoids the often equivocal step of fitting sample bivariate permeability statistics. The model parameters were developed from the new data from the Borden site. The new data included geologic data in much greater abundance than permeability data. There are two scales of unit types delineated in a hierarchy of stratal architecture. Their shapes are complex, not simple layers or lenses. The method facilitated the direct use of both geologic and permeability data, which need not be collocated. The dispersion model developed from these data represents the field‐measured particle displacement variance that occurred in the natural gradient tracer test well. The contributions to time‐dependent macrodispersion by strata at each scale were computed and analyzed independently. This analysis revealed that macrodispersion at the Borden site is primarily controlled by the proportions, and the mean and variance in length of larger‐scale strata of medium sand (M) and strata of fine sand and silt (FZ), with secondary contributions by smaller‐scale strata types occurring within the larger‐scale units. When sampling the pattern in the longitudinal direction, M and FZ couplets repeat at 10 m intervals on average, with a high length variance. To reach a time‐constant macrodispersivity, the stratal length variability must be fully sampled by the plume. The macrodispersivity becomes asymptotic beyond an advective distance of about 60 m, corresponding to about 12 longitudinal transitions between M and FZ unit types.

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.

Numerical analysis of buoyancy effects during the dissolution and transport of oxygenated gasoline in groundwater

Dissolution of oxygenated gasoline, as well as buoyancy‐driven groundwater flow and transport of the multicomponent dissolved phase plumes, is simulated numerically in three dimensions. The simulations are based on a field experiment described by Mocanu (2007) in which three oxygenated gasoline sources were emplaced as nonaqueous phase liquids (NAPLs) below the water table of the shallow sand aquifer at Canadian Forces Base Borden, Ontario. The sources were composed of an ethanol‐free gasoline mixture spiked with 9.8% methyl tert‐butyl ether and 0.2% tert‐butyl alcohol (GMT‐E0), a gasoline with 10% ethanol (E10), and a source with 95% ethanol (E95). The numerical model includes dissolution of gasoline as a NAPL, density‐dependent groundwater flow, advective‐dispersive transport of the dissolved components, and ethanol cosolvency and degradation. Buoyancy effects in the dissolved plumes were compared under a homogeneous hydraulic conductivity field as well as with five realizations of spatially correlated random fields representing the Borden aquifer. The simulations showed that buoyancy was most significant in the E95 source plumes within the homogeneous system, having induced after 150 days a net upward displacement of the local peak concentrations for all but the least soluble component of approximately 1.5 m. The peak rise in ethanol from the GMT‐E0 and E10 plumes was about 0.6 m. The results highlight the importance of shallow monitoring wells when monitoring high oxygenate fraction gasoline spills in groundwater and have implications for assessing mass fluxes and biodegradation rates.

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: A microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600∼800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105–114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.