Transverse vertical dispersion in groundwater and the capillary fringe

Transverse dispersion is the most relevant process in mass transfer of contaminants across the capillary fringe (both directions), dilution of contaminants, and mixing of electron acceptors and electron donors in biodegrading groundwater plumes. This paper gives an overview on literature values of transverse vertical dispersivities alpha(tv) measured at different flow velocities and compares them to results from well-controlled laboratory-tank experiments on mass transfer of trichloroethene (TCE) across the capillary fringe. The measured values of transverse vertical dispersion in the capillary fringe region were larger than in fully saturated media, which is credited to enhanced tortuosity of the flow paths due to entrapped air within the capillary fringe. In all cases, the values observed for alpha(tv) were < 1 mm. The new measurements and the literature values indicate that alpha(tv) apparently declines with increasing flow velocity. The latter is attributed to incomplete diffusive mixing at the pore scale (pore throats). A simple conceptual model, based on the mean square displacement and the pore size accounting for only partial diffusive mixing at increasing flow velocities, shows very good agreement with measured and published data.     

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

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

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.     

Linking a one-dimensional pesticide fate model to a three-dimensional groundwater model to simulate pollution risks of shallow and deep groundwater underlying fractured till

The one-dimensional pesticide fate model MACRO was loose-linked to the three-dimensional discrete fracture/matrix diffusion model FRAC3DVS to describe transport of the pesticide mecoprop in a fractured moraine till and local sand aquifer (5-5.5 m depth) overlying a regional limestone aquifer (16 m depth) at Havdrup, Denmark. Alternative approaches to describe the upper boundary in the groundwater model were examined. Field-scale simulations were run to compare a uniform upper boundary condition with a spatially variable upper boundary derived from Monte-Carlo simulations with MACRO. Plot-scale simulations were run to investigate the influence of the temporal resolution of the upper boundary conditions for fluxes in the groundwater model and the effects of different assumptions concerning the macropore/fracture connectivity between the two models. The influence of within-field variability of leaching on simulated mecoprop concentrations in the local aquifer was relatively small. A fully transient simulation with FRAC3DVS gave 20 times larger leaching to the regional aquifer compared to the case with steady-state water flow, assuming full connectivity with respect to macropores/fractures across the boundary between the two models. For fully transient simulations 'disconnecting' the macropores/fractures at the interface between the two models reduced leaching by a factor 24. A fully connected, transient simulation with FRAC3DVS, with spatially uniform upper boundary fluxes derived from a MACRO simulation with 'effective' parameters is therefore recommended for assessing leaching risks to the regional aquifer, at this, and similar sites.     

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.     

Application of first-order reliability method to modelling the fate and transport of benzene in groundwater

Parameter uncertainty plays a significant role in decision making regarding groundwater contamination and remediation, especially for non-conservative chemicals. This paper presents a probabilistic screening model to accommodate parameter uncertainty in the aquifer media, and physical–chemical parameters, using the first-order reliability method (FORM). The application of the developed model is illustrated on transport of benzene in groundwater. The results matched those obtained using the Monte Carlo simulation method, with a smaller number of functional evaluations. Parametric studies were conducted to estimate the effect of various parameters on the results.     

A Lagrangian approach for modelling turbulent transport and chemistry

A Lagrangian two-particle model for the relative diffusion and mixing of two reactive species is proposed. The model has been tested for consistency in simple geometrical configurations and has been compared to experimental data, Eulerian first- and second-order closure models as well as to other Lagrangian models. The model includes the covariance between the two species and therefore gives better predictions of both diffusion and chemistry than first-order closure models or the one-particle model proposed by Chock and Winkler (1994a,b, Journal of Geophysical Research, 99 D1, 1019–1031, 99 D1, 1033–1041). The model is a generalisation of the model presented by Komori et al. (1991, Journal of Fluid Mechanics 228, 629–659). The results of the calculations, although preliminary in character, indicate that the proposed algorithm is robust and efficient, and yields satisfactory results in turbulence with slow to moderate chemistry.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Iodine enrichment and the underlying mechanism in deep groundwater in the Cangzhou Region,North China

Environmental Science and Pollution Research - The lack of information on the origin and behavior of iodine in deep groundwater restricts the development and use of groundwater resources. To...     

Modelling atmospheric mercury transport and deposition across Europe and the UK

There are inadequate measurements of surface ambient concentrations of mercury species and their deposition rates for the UK deposition budget to be characterized. In order to estimate the overall mercury flux budget for the UK, a simple long-term 1D Lagrangian trajectory model was constructed that treats emissions (1998), atmospheric transformation and deposition across Europe. The model was used to simulate surface concentrations of mercury and deposition across Europe at a resolution of 50 km×50 km and across the UK at 20 km×20 km. The model appeared to perform adequately when compared with the few available measurements, reproducing mean concentrations of elemental gaseous mercury at particular locations and the magnitude of regional gradients. The model showed that 68% of the UK's mercury emissions are exported and 32% deposited within the UK. Of deposition to the UK, 25% originates from the Northern Hemisphere/global background, 41% from UK sources and 33% from other European countries. The total mercury deposition to the UK is in good agreement with other modelling, 9.9 tonne yr⁻¹ cf. 9.0 tonne yr⁻¹, for 1998. However, the attribution differs greatly from the results of other coarser-scale modelling, which allocates 55% of the deposition to the UK from UK sources, 4% from other European countries and 60% from the global background atmosphere. The model was found to be sensitive to the speciation of emissions and the dry deposition velocity of elemental gaseous mercury. The uncertainties and deficiencies are discussed in terms of model parameterization and input data, and measurement data with which models can be validated. There is an urgent requirement for measurements of removal terms, concentrations, and deposition with which models can be parameterized and validated.     

A coupled simulation-optimization approach for groundwater remediation design under uncertainty: An application to a petroleum-contaminated site

This study provides a coupled simulation–optimization approach for optimal design of petroleum-contaminated groundwater remediation under uncertainty. Compared to the previous approaches, it has the advantages of: (1) addressing the stochasticity of the modeling parameters in simulating the flow and transport of NAPLs in groundwater, (2) providing a direct and response-rapid bridge between remediation strategies (pumping rates) and remediation performance (contaminant concentrations) through the created proxy models, (3) alleviating the computational cost in searching for optimal solutions, and (4) giving confidence levels for the obtained optimal remediation strategies. The approach is applied to a practical site in Canada for demonstrating its performance. The results show that mitigating the effects of uncertainty on optimal remediation strategies (through enhancing the confidence level) would lead to the rise of remediation cost due to the increase in the total pumping rate.     

Modelling the geochemical fate and transport of wastewater-derived phosphorus in contrasting groundwater systems

A 1D reactive transport model (RTM) is used to obtain a mechanistic understanding of the fate of phosphorus (P) in the saturated zone of two contrasting aquifer systems. We use the field data from two oxic, electron donor-poor, wastewater-impacted, sandy Canadian aquifers, (Cambridge and Muskoka sites) as an example of a calcareous and non-calcareous groundwater system, respectively, to validate our reaction network. After approximately 10 years of wastewater infiltration, P is effectively attenuated within the first 10 m down-gradient of the source mainly through fast sorption onto calcite and Fe oxides. Slow, kinetic sorption contributes further to P removal, while precipitation of phosphate minerals (strengite, hydroxyapatite) is quantitatively unimportant in the saturated zone. Nitrogen (N) dynamics are also considered, but nitrate behaves essentially as a conservative tracer in both systems. The model-predicted advancement of the P plume upon continued wastewater discharge at the calcareous site is in line with field observations. Model results suggest that, upon removal of the wastewater source, the P plume at both sites will persist for at least 20 years, owing to desorption of P from aquifer solids and the slow rate of P mineral precipitation. Sensitivity analyses for the non-calcareous scenario (Muskoka) illustrate the importance of the sorption capacity of the aquifer solids for P in modulating groundwater N:P ratios in oxic groundwater. The model simulations predict the breakthrough of groundwater with high P concentrations and low N:P ratios after 17 years at 20 m from the source for an aquifer with low sorption capacity (<0.02% w/w Fe(OH)(3)). In this type of system, denitrification plays a minor role in lowering the N:P ratios because it is limited by the availability of labile dissolved organic matter.     

Modeling riverine nutrient transport to the Baltic Sea: a large-scale approach

We developed for the first time a catchment model simulating simultaneously the nutrient land-sea fluxes from all 105 major watersheds within the Baltic Sea drainage area. A consistent modeling approach to all these major watersheds, i.e., a consistent handling of water fluxes (hydrological simulations) and loading functions (emission data), will facilitate a comparison of riverine nutrient transport between Baltic Sea subbasins that differ substantially. Hot spots of riverine emissions, such as from the rivers Vistula, Oder, and Daugava or from the Danish coast, can be easily demonstrated and the comparison between these hot spots, and the relatively unperturbed rivers in the northern catchments show decisionmakers where remedial actions are most effective to improve the environmental state of the Baltic Sea, and, secondly, what percentage reduction of riverine nutrient loads is possible. The relative difference between measured and simulated fluxes during the validation period was generally small. The cumulative deviation (i.e., relative bias) [Sigma(Simulated - Measured)/Sigma Measured x 100 (%)] from monitored water and nutrient fluxes amounted to +8.2% for runoff, to -2.4% for dissolved inorganic nitrogen, to +5.1% for total nitrogen, to +13% for dissolved inorganic phosphorus and to +19% for total phosphorus. Moreover, the model suggests that point sources for total phosphorus compiled by existing pollution load compilations are underestimated because of inconsistencies in calculating effluent loads from municipalities.     

Using the multiple cell balance method to solve the problem of two-dimensional groundwater flow and contaminant transport with nonequilibrium sorption

The problem of large-scale contamination of groundwater by relatively low levels of organic contaminants is most frequently addressed by extracting and treating the impacted groundwater. This pump-and-treat strategy is often unsuccessful because of difficulties encountered in recovering the contaminants from relatively immobile zones within the porous medium. These zones can exist at the particle scale, as intraparticle or intra-aggregate porosity, and at the larger scales, as low-permeability layers or lenses interspersed in substantially more permeable layers. This work focuses on achieving an efficient numerical solution to a system of groundwater flow and contaminant transport equations that sufficiently captures the dynamics of slow desorption in a two-dimensional porous medium. The conceptual model and governing equations are presented. A numerical method for solving the governing equations, the upstream-weighted, multiple cell balance (UMCB) method, is proposed. The UMCB algorithm has been employed previously for the case of solute transport with equilibrium sorption, and is extended here to the nonequilibrium case. The approach employs a finite-element basis function and a finite-difference local mass balance, and is designed to reduce computational and storage requirements, while minimizing the mass balance error. The computational grid is formed by division of the flow domain into triangular elements. An invented node at the center of each element divides the element into three subtriangular regions. By linking the center of each triangular element and the mid-point of each elemental side, a multiangular region, referred to as an exclusive subdomain, is defined. The discretized system of governing equations is derived from the integral form that describes the mass balance in the exclusive subdomain of each node. The paper details the application of the numerical method, and demonstrates that the method is reasonably accurate and computationally efficient for a two-dimensional domain subject to nonequilibrium sorption.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

A triple-continuum approach for modeling flow and transport processes in fractured rock

This paper presents a triple-continuum conceptual model for simulating flow and transport processes in fractured rock. Field data collected from the unsaturated zone of Yucca Mountain, a repository site of high-level nuclear waste, show a large number of small-scale fractures. The effect of these small fractures has not been considered in previous modeling investigations within the context of a continuum approach. A new triple-continuum model (consisting of matrix, small-fracture, and large-fracture continua) has been developed to investigate the effect of these small fractures. This paper derives the model formulation and discusses the basic triple-continuum behavior of flow and transport processes under different conditions, using both analytical solutions and numerical approaches. The simulation results from the site-scale model of the unsaturated zone of Yucca Mountain indicate that these small fractures may have an important effect on radionuclide transport within the mountain.     

Contaminant transport in groundwater in the presence of colloids and bacteria: Model development and verification

Colloids and bacteria (microorganisms) naturally exist in groundwater aquifers and can significantly impact contaminant migration rates. A conceptual model is first developed to account for the different physiochemical and biological processes, reaction kinetics, and different transport mechanisms of the combined system (contaminant–colloids–bacteria). All three constituents are assumed to be reactive with the reactions taking place between each constituent and the porous medium and also among the different constituents. A general linear kinetic reaction model is assumed for all reactive processes considered. The mathematical model is represented by fourteen coupled partial differential equations describing mass balance and reaction processes. Two of these equations describe colloid movement and reactions with the porous medium, four equations describe bacterial movement and reactions with colloids and the porous medium, and the remaining eight equations describe contaminant movement and its reactions with bacteria, colloids, and the porous medium. The mass balance equations are numerically solved for two-dimensional groundwater systems using a third-order, total variance-diminishing scheme (TVD) for the advection terms. Due to the complex coupling of the equations, they are solved iteratively each time step until a convergence criterion is met. The model is tested against experimental data and the results are favorable.     

Soil column experiments used as a means to assess transport, sorption, and biodegradation of pesticides in groundwater

Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 micro g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br(-) breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.     

Soil column experiments used as a means to assess transport,sorption, and biodegradation of pesticides in groundwater

Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 μ g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br^? breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.