Modeling of non-reactive solute transport in fractured clayey till during variable flow rate and time

Fractures and biopores can act as preferential flow paths in clay aquitards and may rapidly transmit contaminants into underlying aquifers. Reliable numerical models for assessment of groundwater contamination from such aquitards are needed for planning, regulatory and remediation purposes. In this investigation, high resolution preferential water-saturated flow and bromide transport data were used to evaluate the suitability of equivalent porous medium (EPM), dual porosity (DP) and discrete fracture/matrix diffusion (DFMD) numerical modeling approaches for assessment of flow and non-reactive solute transport in clayey till. The experimental data were obtained from four large undisturbed soil columns (taken from 1.5 to 3.5 m depth) in which biopores and channels along fractures controlled 96-99% of water-saturated flow. Simulating the transport data with the EPM effective porosity model (FRACTRAN in EPM mode) was not successful because calibrated effective porosity for the same column had to be varied up to 1 order of magnitude in order to simulate solute breakthrough for the applied flow rates between 11 and 49 mm/day. Attempts to simulate the same data with the DP models CXTFIT and MODFLOW/MT3D were also unsuccessful because fitted values for dispersion, mobile zone porosity, and mass transfer coefficient between mobile and immobile zones varied several orders of magnitude for the different flow rates, and because dispersion values were furthermore not physically realistic. Only the DFMD modeling approach (FRACTRAN in DFMD mode) was capable to simulate the observed changes in solute transport behavior during alternating flow rate without changing values of calibrated fracture spacing and fracture aperture to represent the macropores.     

A model for non-specific toxicity with aquatic organisms over relatively long periods of exposure time

Experimental data have shown that the internal lethal concentrations of halobenzenes for aquatic organisms decreased with exposure time. In this paper, a model based on the concept of life expectancy reduction was developed to describe this relationship. The model was verified with experimental data for fish (Gambusia affinis) and juvenile crab (Porturius pelagicus(L)). It is proposed that long term non-specific toxicity can be measured as the reduction of the life expectancy of the exposed organism per unit internal concentration (or volume fraction) of the toxic compound. The model can be used to estimate internal lethal concentration at any given exposure period and vice versa. The model can also be used to estimate chronic values of the internal concentration, of the toxicants. It provides a useful tool for assessment of environmental risk of organic compounds in aquatic ecosystems.     

Numerical modeling of coupled variably saturated fluid flow and reactive transport with fast and slow chemical reactions

The couplings among chemical reaction rates, advective and diffusive transport in fractured media or soils, and changes in hydraulic properties due to precipitation and dissolution within fractures and in rock matrix are important for both nuclear waste disposal and remediation of contaminated sites. This paper describes the development and application of LEHGC2.0, a mechanistically based numerical model for simulation of coupled fluid flow and reactive chemical transport, including both fast and slow reactions in variably saturated media. Theoretical bases and numerical implementations are summarized, and two example problems are demonstrated. The first example deals with the effect of precipitation/dissolution on fluid flow and matrix diffusion in a two-dimensional fractured media. Because of the precipitation and decreased diffusion of solute from the fracture into the matrix, retardation in the fractured medium is not as large as the case wherein interactions between chemical reactions and transport are not considered. The second example focuses on a complicated but realistic advective-dispersive-reactive transport problem. This example exemplifies the need for innovative numerical algorithms to solve problems involving stiff geochemical reactions.     

A remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation efficiency and timeframe. A relatively simple approach is used to link the fermentation of the electron donor soybean oil to the sequential dechlorination of trichloroethene (TCE) while considering redox conditions and the heterogeneous clay till system (clay till matrix, fractures and sand stringers). The model is tested on lab batch experiments and applied to describe sediment core samples from a TCE-contaminated site. Model simulations compare favorably to field observations and demonstrate that dechlorination may be limited to narrow bioactive zones in the clay matrix around fractures and sand stringers. Field scale simulations show that the injected donor is expected to be depleted after 5 years, and that without donor re-injection contaminant rebound will occur in the high permeability zones and the mass removal will stall at 18%. Long remediation timeframes, if dechlorination is limited to narrow bioactive zones, and the need for additional donor injections to maintain dechlorination activity may limit the efficiency of ERD in low-permeability media. Future work should address the dynamics of the bioactive zones, which is essential to understand for predictions of long term mass removal.     

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.     

Migration of colloids in discretely fractured porous media: effect of colloidal matrix diffusion

Numerical simulations of colloid transport in discretely fractured porous media were performed to investigate the importance of matrix diffusion of colloids as well as the filtration and remobilization of colloidal particles in both the fractures and porous matrix. To achieve this objective a finite element numerical code entitled COLDIFF was developed. The processes that COLDIFF takes into account include advective-dispersive transport of colloids, filtration and remobilization of colloidal particles in both fractures and porous matrix, and diffusive interactions of colloids between the fractures and porous matrix. Three sets of simulations were conducted to examine the importance of parameters and processes controlling colloid migration. First, a sensitivity analysis was performed using a porous block containing a single fracture to determine the relative importance of various phenomenological coefficients on colloid transport. The primary result of the analysis showed that the porosity of the matrix and the process of colloid filtration in fractures play important roles in controlling colloid migration. Second, simulations were performed to replicate and examine the results of a laboratory column study using a fractured shale saprolite. Results of this analysis showed that the filtration of colloidal particles in the porous matrix can greatly affect the tailing of colloid concentrations after the colloid source was removed. Finally, field-scale simulations were performed to examine the effect of matrix porosity, fracture filtration and fracture remobilization on long-term colloid concentration and migration distance. The field scale simulations indicated that matrix diffusion and fracture filtration can significantly reduce colloid migration distance. Results of all three analyses indicated that in environments where porosity is relatively high and colloidal particles are small enough to diffuse out of fractures, the characteristics of the porous matrix that affect colloid transport become more important than those of the fracture network. Because the properties of the fracture network tend to have greater uncertainty due to difficulties in their measurement relative to those of the porous matrix, prediction uncertainties associated with colloid transport in discretely fractured porous media may be reduced.     

Numerical analysis of water and solute transport in variably-saturated fractured clayey till

This study numerically investigates the influence of initial water content and rain intensities on the preferential migration of two fluorescent tracers, Acid Yellow 7 (AY7) and Sulforhodamine B (SB), through variably-saturated fractured clayey till. The simulations are based on the numerical model HydroGeoSphere, which solves 3D variably-saturated flow and solute transport in discretely-fractured porous media. Using detailed knowledge of the matrix, fracture, and biopore properties, the numerical model is calibrated and validated against experimental high-resolution tracer images/data collected under dry and wet soil conditions and for three different rain events. The model could reproduce reasonably well the observed preferential migration of AY7 and SB through the fractured till, although it did not capture the exact depth of migration and the negligible impact of the dead-end biopores in a near-saturated matrix. A sensitivity analysis suggests fast flow mechanisms and dynamic surface coating in the biopores, and the presence of a plough pan in the till.     

Interpretation of injection-withdrawal tracer experiments conducted between two wells in a large single fracture

Tracer experiments conducted using a flow field established by injecting water into one borehole and withdrawing water from another are often used to establish connections and investigate dispersion in fractured rock. As a result of uncertainty in the uniqueness of existing models used for interpretation, this method has not been widely used to investigate more general transport processes including matrix diffusion or advective solute exchange between mobile and immobile zones of fluid. To explore the utility of the injection-withdrawal method as a general investigative tool and with the intent to resolve the transport processes in a discrete fracture, two tracer experiments were conducted using the injection-withdrawal configuration. The experiments were conducted in a fracture which has a large aperture (>500 microm) and horizontally pervades a dolostone formation. One experiment was conducted in the direction of the hydraulic gradient and the other in the direction opposite to the natural gradient. Two tracers having significantly different values of the free-water diffusion coefficient were used. To interpret the experiments, a hybrid numerical-analytical model was developed which accounts for the arcuate shape of the flow field, advection-dispersion in the fracture, diffusion into the matrix adjacent to the fracture, and the presence of natural flow in the fracture. The model was verified by comparison to a fully analytical solution and to a well-known finite-element model. Interpretation of the tracer experiments showed that when only one tracer, advection-dispersion, and matrix diffusion are considered, non-unique results were obtained. However, by using multiple tracers and by accounting for the presence of natural flow in the fracture, unique interpretations were obtained in which a single value of matrix porosity was estimated from the results of both experiments. The estimate of porosity agrees well with independent measurements of porosity obtained from core samples. This suggests that: (i) the injection-withdrawal method is a viable tool for the investigation of general transport processes provided all relevant experimental conditions are considered and multiple conservative tracers are used; and (ii) for the conditions of the experiments conducted in this study, the dominant mechanism for exchange of solute between the fracture and surrounding medium is matrix diffusion.     

Long-term oxygen depletion from infiltrating groundwaters: model development and application to intra-glaciation and glaciation conditions

Processes that control the redox conditions in deep groundwaters have been studied. The understanding of such processes in a long-term perspective is important for the safety assessment of a deep geological repository for high-level nuclear waste. An oxidising environment at the depth of the repository would increase the solubility and mobility of many radionuclides, and increase the potential risk for radioactive contamination at the ground surface. Proposed repository concepts also include engineered barriers such as copper canisters, the corrosion of which increases considerably in an oxidising environment compared to prevailing reducing conditions. Swedish granitic rocks are typically relatively sparsely fractured and are best treated as a dual-porosity medium with fast flowing channels through fractures in the rock with a surrounding porous matrix, the pores of which are accessible from the fracture by diffusive transport. Highly simplified problems have been explored with the aim to gain understanding of the underlying transport processes, thermodynamics and chemical reaction kinetics. The degree of complexity is increased successively, and mechanisms and processes identified as of key importance are included in a model framework. For highly complex models, analytical expressions are not fully capable of describing the processes involved, and in such cases the solutions are obtained by numerical calculations. Deep in the rock the main source for reducing capacity is identified as reducing minerals. Such minerals are found inside the porous rock matrix and as infill particles or coatings in fractures in the rock. The model formulation also allows for different flow modes such as flow along discrete fractures in sparsely fractured rocks and along flowpaths in a fracture network. The scavenging of oxygen is exemplified for these cases as well as for more comprehensive applications, including glaciation considerations. Results show that chemical reaction kinetics control the scavenging of oxygen during a relatively short time with respect to the lifetime of the repository. For longer times the scavenging of oxygen is controlled by transport processes in the porous rock matrix. The penetration depth of oxygen along the flowpath depends largely on the hydraulic properties, which may vary significantly between different locations and situations. The results indicate that oxygen, in the absence of easily degradable organic matter, may reach long distances along a flow path during the life-time of the repository (hundreds to thousands of metres in a million years depending on e.g. hydraulic properties of the flow path and the availability of reducing capacity). However, large uncertainties regarding key input parameters exist leading to the conclusion that the results from the model must be treated with caution pending more accurate and validated data. Ongoing and planned experiments are expected to reduce these uncertainties, which are required in order to make more reliable predictions for a safety assessment of a nuclear waste repository.     

An urban trajectory model for sulfur in Asian megacities: model concepts and preliminary application

This paper explores the adaptation of a regional Lagrangian approach for making long-term simulations of SO₂ and sulfate ambient concentrations at the resolution needed for health effects risk assessment in Asian megacities and their surroundings. A Lagrangian trajectory model (UR-BAT) is described which simulates transport and diffusion of sulfur within and near urban areas, originating from area and major point sources. The long-range contribution is accounted for by the ATMOS model, simulating all Asian sources. The model has been applied to Beijing and Bombay, by using preliminary emission figures, and the results have been compared with available monitoring data. The computed concentrations in different cities are in the correct range, indicating the potential use of the model in an integrated assessment framework such as RAINS-Asia.     

Two-dimensional distribution of microbial activity and flow patterns within naturally fractured chalk

The two-dimensional distribution of flow patterns and their dynamic change due to microbial activity were investigated in naturally fractured chalk cores. Long-term biodegradation experiments were conducted in two cores ( approximately 20 cm diameter, 31 and 44 cm long), intersected by a natural fracture. 2,4,6-tribromophenol (TBP) was used as a model contaminant and as the sole carbon source for aerobic microbial activity. The transmissivity of the fractures was continuously reduced due to biomass accumulation in the fracture concurrent with TBP biodegradation. From multi-tracer experiments conducted prior to and following the microbial activity, it was found that biomass accumulation causes redistribution of the preferential flow channels. Zones of slow flow near the fracture inlet were clogged, thus further diverting the flow through zones of fast flow, which were also partially clogged. Quantitative evaluation of biodegradation and bacterial counts supported the results of the multi-tracer tests, indicating that most of the bacterial activity occurs close to the inlet. The changing flow patterns, which control the nutrient supply, resulted in variations in the concentrations of the chemical constituents (TBP, bromide and oxygen), used as indicators of biodegradation.     

Two-phase flow and transport in a single fracture-porous medium system

The prognosis for the remediation of contaminated fractured media is much worse than that for more homogeneous units. Fractures act as conduits for the flow of dense non-aqueous phase liquids (DNAPLs), while diffusion is responsible for the storage of dissolved mass in the surrounding matrix. A numerical model incorporating aqueous phase transport in a variable-aperture fracture and its surrounding matrix is developed and coupled with an existing two-phase flow model. The processes of transient two-phase flow, non-equilibrium dissolution, advective–dispersive transport in the fracture, and three-dimensional matrix diffusion are included in the model. Results from various investigations show that the DNAPL distribution is very sensitive to variations in aperture within a single fracture. Diffusion-controlled mass removal from both the matrix and from the hydraulically inaccessible zones within the fracture itself result in extremely large time frames for significant mass removal from these systems. Success in aqueous phase mass removal from the matrix is very sensitive to the effective fracture spacing. The hydraulic gradient in the fracture only affects the amount of water removed from the system, and does not greatly affect the amount of time required to remove the contaminant mass from the matrix. The ability to remove mass is somewhat sensitive to the porosity and effective matrix diffusion coefficient over the range of expected values.     

Predictive modelling of NAPL injection tests in variable aperture spatially correlated fractures.

In preparation for a field experiment where a NAPL will be injected into a fractured sandstone aquifer, a 2D invasion percolation model of DNAPL migration in a single horizontal fracture with varying aperture has been developed. This simulation investigated the effect of spatially correlated fracture aperture fields on pressure-saturation relationships as a function of variable aperture mean, standard deviation, and spatial correlation statistics under hydrostatic conditions. Results from spatially correlated variable aperture fields can be significantly different from random fields. Longer ranges decreased entry pressures and higher standard deviations decreased nonwetting phase saturations. Mean aperture is the major control on displacement pressure, entry pressure and the form of the pressure-saturation curve. Simulation results using statistical parameters for a variable aperture natural sandstone fracture as described by Yeo et al. [International Journal of Rock Mechanics and Mining Sciences 35 (1998) 1051] closely resemble a Brooks-Corey pressure-saturation function, and exhibit a distinct entry pressure followed by a rapid increase in nonwetting phase saturation. Graphical estimates of entry pressure provide a good approximation of the critical aperture controlling the formation of a continuous nonwetting phase pathway in a variable aperture fracture. Consequently, we show that multiphase flow concepts developed for porous media can successfully be applied to variable aperture fractures. Entry pressure correlates well to the mean aperture in these simulations when using a Gaussian distribution of fracture aperture. Interpreted aperture distributions from NAPL injection experiments do not fit the true distribution well at low nonwetting phase saturations, but do at higher saturations above the entry pressure. Consequently, true, mechanical aperture variation within a fracture plane cannot be determined from NAPL injection experiments either in the field or laboratory.     

Characterization of flow and transport processes within the unsaturated zone of Yucca Mountain, Nevada, under current and future climates

This paper presents a large-scale modeling study characterizing fluid flow and tracer transport in the unsaturated zone of Yucca Mountain, Nevada, a potential repository site for storing high-level radioactive waste. The study has been conducted using a three-dimensional numerical model, which incorporates a wide variety of field data and takes into account the coupled processes of flow and transport in the highly heterogeneous, unsaturated fractured porous rock. The modeling approach is based on a dual-continuum formulation of coupled multiphase fluid and tracer transport through fractured porous rock. Various scenarios of current and future climate conditions and their effects on the unsaturated zone are evaluated to aid in the assessment of the proposed repository's system performance using different conceptual models. These models are calibrated against field-measured data. Model-predicted flow and transport processes under current and future climates are discussed.     

Risk assessment and prioritisation of contaminated sites on the catchment scale

Contaminated sites pose a significant threat to groundwater resources worldwide. Due to limited available resources a risk-based prioritisation of the remediation efforts is essential. Existing risk assessment tools are unsuitable for this purpose, because they consider each contaminated site separately and on a local scale, which makes it difficult to compare the impact from different sites. Hence a modelling tool for risk assessment of contaminated sites on the catchment scale has been developed. The CatchRisk screening tool evaluates the risk associated with each site in terms of its ability to contaminate abstracted groundwater in the catchment. The tool considers both the local scale and the catchment scale. At the local scale, a flexible, site specific leaching model that can be adjusted to the actual data availability is used to estimate the mass flux over time from identified sites. At the catchment scale, a transport model that utilises the source flux and a groundwater model covering the catchment is used to estimate the transient impact on the supply well. The CatchRisk model was tested on a groundwater catchment for a waterworks north of Copenhagen, Denmark. Even though data scarcity limited the application of the model, the sites that most likely caused the observed contamination at the waterworks were identified. The method was found to be valuable as a basis for prioritising point sources according to their impact on groundwater quality. The tool can also be used as a framework for testing hypotheses on the origin of contamination in the catchment and for identification of unknown contaminant sources.     

Experimental study of the transport properties of rough self-affine fractures

An experimental study of the transport properties of fluid-saturated joints composed of two complementary rough fracture surfaces, translated with respect to each other and brought in contact, is reported. Quantitative roughness measurements on different fractured granite samples show that the surfaces have a self-affine geometry from which the dependence of the mean aperture on the relative displacement of fracture surfaces kept in contact can be predicted. Variations of the hydraulic and electrical conductances of the joint are measured as functions of its mean aperture. A simple parallel plane model accounts for the global trend of the measurements, but significant deviations are observed when a relative lateral displacement of the surfaces is introduced. A theoretical analysis of their origin shows that they are due both to the randomness of the aperture field and to a nonzero local slope of the surface near the injection hole; the corresponding conductivity fluctuation amplitudes have power law and linear variations with the lateral displacement, and are enhanced by the radial injection geometry.     

Modeling field-scale multiple tracer injection at a low-level waste disposal site in fractured rocks: effect of multiscale heterogeneity and source term uncertainty on conceptual understanding of mass transfer processes

Multiple factors may affect the scale-up of laboratory multi-tracer injection into structured porous media to the field. Under transient flow conditions and with multiscale heterogeneities in the field, previous attempts to scale-up laboratory experiments have not answered definitely the questions about the governing mechanisms and the spatial extent of the influence of small-scale mass transfer processes such as matrix diffusion. The objective of this research is to investigate the effects of multiscale heterogeneity, mechanistic and site model conceptualization, and source term density effect on elucidating and interpreting tracer movement in the field. Tracer release and monitoring information previously obtained in a field campaign of multiple, conservative tracer injection under natural hydraulic gradients at a low-level waste disposal site in eastern Tennessee, United States, is used for the research. A suite of two-pore-domain, or fracture-matrix, groundwater flow and transport models are calibrated and used to conduct model parameter and prediction uncertainty analyses. These efforts are facilitated by a novel nested Latin-hypercube sampling technique. Our results verify, at field scale, a multiple-pore-domain, multiscale mechanistic conceptual model that was used previously to interpret only laboratory observations. The results also suggest that, integrated over the entire field site, mass flux rates attributable to small-scale mass transfer are comparable to that of field-scale solute transport. The uncertainty analyses show that fracture spacing is the most important model parameter and model prediction uncertainty is relatively higher at the interface between the preferred flow path and its parent bedrock. The comparisons of site conceptual models indicate that the effect of matrix diffusion may be confined to the immediate neighborhood of the preferential flow path. Finally, because the relatively large amount of tracer needed for field studies, it is likely that source term density effect may exaggerate or obscure the effect of matrix diffusion on the movement of tracers from the preferred flow path into the bedrock.     

Bioassays with Vibrio fischeri for the assessment of delayed toxicity

The standardized bioluminescence assay with Vibrio fischeri underestimates the aquatic toxicity of chemicals which interfere with metabolic pathways supporting long term processes like growth and reproduction due to its short incubation time (30 min). Therefore this short term assay was compared with two alternative bioassays with prolonged incubation times using the same test organism: the growth inhibition assay (7 h) and the long term bioluminescence assay (24 h). Two sets of compounds were selected to reflect acute and delayed toxicity. The first group comprised pentachlorophenol, dodecylpyridiniumbromide and 3,4-dichloroaniline and the second nalidixic acid, chloramphenicol and streptomycinsulfate. The effects of compounds with acute toxicity are determined with similar sensitivity in all bioassays. Substances with delayed toxicity show only minor or no toxicities in the standardized short term bioassay but severe effects in both long term bioassays independent of the parameter used. It is concluded that the standardized short term bioluminescence assay exhibits serious limitations for the assessment of aquatic toxicity. The long term bioassays, however, may help to overcome these limitations.     

Comparison of computer simulations of total lung deposition to human subject data in healthy test subjects

A mathematical model was used to predict the deposition fractions (DF) of PM within human lungs. Simulations using this computer model were previously validated with human subject data and were used as a control case. Human intersubject variation was accounted for by scaling the base lung morphology dimensions based on measured functional residual capacity (FRC) values. Simulations were performed for both controlled breathing (tidal volumes [VT] of 500 and 1000 mL, respiratory times [T] from 2 to 8 sec) and spontaneous breathing conditions. Particle sizes ranged from 1 to 5 microns. The deposition predicted from the computer model compared favorably with the experimental data. For example, when VT = 1000 mL and T = 2 sec, the error was 1.5%. The errors were slightly higher for smaller tidal volumes. Because the computer model is deterministic (i.e., derived from first principles of physics), the model can be used to predict deposition fractions for a range of situations (i.e., for different ventilatory parameters and particle sizes) for which data are not available. Now that the model has been validated, it may be applied to risk assessment efforts to estimate the inhalation hazards of airborne pollutants.     

Data assimilation in the atmospheric dispersion model for nuclear accident assessments

Uncertainty factors in atmospheric dispersion models may influence the reliability of model prediction. The ability of a model in assimilating measurement data will be helpful to improve model prediction. In this paper, data assimilation based on ensemble Kalman filter (EnKF) is introduced to a Monte Carlo atmospheric dispersion model (MCADM) designed for assessment of consequences after an accident release of radionuclides. Twin experiment has been performed in which simulated ground-level dose rates have been assimilated. Uncertainties in the source term and turbulence intensity of wind field are considered, respectively. Methodologies and preliminary results of the application are described. It is shown that it is possible to reduce the discrepancy between the model forecast and the true situation by data assimilation. About 80% of error caused by the uncertainty in the source term is reduced, and the value for that caused by uncertainty in the turbulence intensity is about 50%.