Application of Unknown Groundwater Pollution Source Release History Estimation Methodology to Distributed Sources Incorporating Surface-Groundwater Interactions

Sources of contamination of groundwater are often difficult to characterize. However, it is essential for effective remediation of polluted groundwater resources. This study demonstrates an application of the linked simulation-optimization based methodology to estimate the release history from spatially distributed sources of pollution at an illustrative abandoned mine-site. In linked simulation-optimization approaches a numerical groundwater flow and transport simulation model is linked to the optimization model. In this study, topographic and geologic characteristics of the abandoned mine-site were simulated using a three-dimensional (3D) numerical groundwater flow model. Transport of contaminant in the groundwater was simulated using a 3D transient advective-dispersive contaminant transport model. Adsorption or chemical reaction of the contaminant was not considered in the contaminant transport model. Adaptive simulated annealing (ASA) was employed for solving the optimization problem. An optimization algorithm generates the candidate solutions corresponding to various unknown groundwater source characteristics. The candidate solutions are used as input in the numerical groundwater transport simulation model to generate the concentration of pollutant in the study area. This information is used to calculate the objective function value, which is utilized by the optimization algorithm to improve the candidate solution. This process continues until an optimal solution is obtained. Optimal solutions obtained in this study show that the linked simulation-optimization based methodology is potentially applicable for the characterization of spatially distributed pollutant sources, typically present at abandoned mine-sites.     

A screening method for preliminary assessment of risk to groundwater from land-applied chemicals

A simple mathematical model for initial screening is presented that can aid in evaluating the relative risk to groundwater from applying nonpolar synthetic organic chemicals to soil. The basic premise is that the magnitude of the quotient of the chemical concentration of the water entering the aquifer and the maximum allowable concentration (as established by EPA or Health Departments) represents the health risk of a chemical. The chemical concentration of the soil water is estimated based on conservative, simplifying assumptions and requires only readily available data such as: basic soil properties (organic matter and saturated hydraulic conductivity), organic chemical properties (octanol-water partition coefficient and degradation rate) and environmental factors (recharge rate and depth to groundwater).The methodology was applied to assess the relative risk of organic chemicals in municipal sewage sludge and pesticides applied to agricultural land. The results are realistic.     

Long-range transport potential of semivolatile organic chemicals in coupled air-water systems

Ongoing deliberations on the regulation of semivolatile organic chemicals require the assessment of chemical transport in atmospheric and marine systems. The characteristic travel distance was proposed as a measure for the transport potential in air and water. However, the existing definition treats the transport processes separately. It is shown that combined transport in coupled air-ocean systems can accelerate the overall transport into remote regions. Concentration ratios in air and water change with distance from sources depending on the initial concentration ratio and on the difference between the transport velocities. A measure is suggested facilitating the chemical screening with respect to transport potentials in such air-ocean systems. A case study for alpha and gamma-hexachlorocyclohexane shows that the suggested measure qualitatively reveals the transport potentials of these chemicals and exemplifies possible concentration patterns.     

Landfill Gas Effects on Groundwater Samples at a Municipal Solid Waste Facility

A study was performed to determine the source of low concentrations of volatile organic compounds (VOCs) detected in groundwater samples at a solid waste management facility. The affected wells were identified as hydraulically upgradient of an old unlined facility, but downgradient of a new clay-lined landfill. These monitoring wells are close to both sites. Subsurface landfill gas migration was identified after a low permeability cap was installed on the older site. Subsurface gas pressure was monitored to identify horizontal landfill gas migration. Monitoring well headspace gases were evaluated to identify depressed oxygen concentrations and methane because of landfill gas migration into the well. Monitoring well headspace gas VOC concentrations were compared to groundwater VOC concentrations to determine the direction of phase transfer. A ratio above 1.0 of the observed well headspace gas concentration of a VOC to the concentration that would be in equilibrium with the groundwater concentration indicates gas-to-water phase transfer within the well. For the major gas-phase and aqueous-phase VOC, cis-1,2-dichloroethene, gas-to-water phase transfer is clearly indicated from the data for two of the four wells. Fifteen other VOCs were detected in monitoring well headspace gases but not in groundwater samples from the four wells studied. Only one compound in one well was detected in the groundwater sample but not in the headspace gases, and only one compound in one well was detected in both matrices at concentrations that suggested water-to-gas phase transfer. This study suggests that if landfill gas is suspected as the source of detected VOCs, monitoring well construction and stratigraphy are important considerations when attempting to differentiate between groundwater contamination by landfill gas and contamination from other sources.     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.     

A large-scale experiment on mass transfer of trichloroethylene from the unsaturated zone of a sandy aquifer to its interfaces

A large-scale experiment was conducted to investigate the transport of trichloroethylene (TCE) vapors in the unsaturated zone and to determine the mass transfer to the groundwater and the atmosphere. The experiment involved injection of 5 1 of TCE in the unsaturated zone under controlled conditions, with multidepth sampling of gas and water through the unsaturated zone and across the capillary zone into underlying groundwater. The mass transfer of TCE vapors from the vadose zone to the atmosphere was quantified using a vertical flux chamber. A special soil water sampler was used to monitor transport across the capillary fringe. Experimental data indicated that TCE in the unsaturated zone was mainly transported to the atmosphere and this exchange reduced significantly the potential for groundwater pollution. The maximum measured TCE flux to the atmosphere was about 3 g/m(2)/day. Observed and calculated fluxes based on vertical TCE vapor concentration gradients and Fick's law were in good agreement. This confirms that TCE vapor transport under the experimental conditions was governed essentially by molecular diffusion. TCE vapors also caused a lower, but significant contamination of the underlying groundwater by dispersion across the capillary fringe with a corresponding maximum flux of about 0.1 g/m(2)/day. This mass transfer to groundwater is partly uncertain due to an inadvertent entry of some nonaqueous phase liquid (NAPL) from the source area into the saturated zone. Application of an analytical solution to estimate the TCE flux from the unsaturated zone to the groundwater indicated that this phenomenon is not only influenced by molecular diffusion but also by vertical dispersion. The mass balance indicates that, under the given experimental conditions (e.g. proximity of the source emplacement relative to the soil surface, relatively high permeable porous medium), nearly 95% of the initial TCE mass was transferred to the atmosphere.     

One-at-a-time sensitivity analysis of pollutant loadings to subsurface properties for the assessment of soil and groundwater pollution potential

Chemical leak was numerically simulated for four chemical substances: benzene (light non-aqueous phase liquid (NAPL)), tetrachloroethylene (dense NAPL), phenol (soluble in water), and pentachlorophenol (white crystalline solid) in a hypothetical subsurface leak situation using a multiphase compositional transport model. One metric ton of chemical substances was assumed to leak at a point 3.51 m above the water table in a homogeneous unconfined aquifer which had the depth to water table of 7.135 m, the hydraulic gradient of 0.00097, the recharge rate of 0.7 mm/day, and the permeability of 2.92?×?10^?10 m². For comparison, surface spill scenarios, which had a long pathway from source to the water table, were simulated. Using the model results, point-source pollutant loadings to soil and groundwater were calculated by multiplying mass, impact area, and duration above and below the water table respectively. Their sensitivity to subsurface properties (depth to water table, recharge rate, porosity, organic carbon content, decay rate, hydraulic gradient, capillary pressure, relative permeability, permeability) was analyzed, with changing each parameter within acceptable ranges. The study result showed that the pollutant loading to groundwater was more sensitive to the subsurface properties than the pollutant loading to soil. Decay rate, groundwater depth, hydraulic gradient and porosity were influential to pollutant loadings. The impact of influential parameters on pollutant loadings was nonlinear. The dominant subsurface properties of pollution loadings (e.g., decay rate, groundwater depth, hydraulic gradient, and porosity for groundwater) also affect the vulnerability, and the subsurface pollutant loadings defined in this study are dependent on chemical properties as well, which indicates that the influential hydrogeological and physicochemical parameters to pollutant loadings can be used for pollution potential assessment. The contribution of this work is the suggestion that the sensitivity of pollutant loadings can be used for pollution potential assessment. Soil and groundwater pollution potential of chemicals are discussed altogether for leak scenarios. A physics-based model is used to understand the impact of subsurface properties on the fate and transport of chemicals above and below the water table, and consequently their impact on the pollutant loading to soil and groundwater.

     

Numerical methods for describing chemical transport in the unsaturated zone of the subsurface

Finite-difference and finite-element methods of approximation have been extended to solve the one-dimensional nonlinear partial differential equations that describe the simultaneous transport of heat, moisture and chemical in the unsaturated zone. Especially for chemical transport, nodal spacing criteria are required to minimize numerical dispersion and oscillatory behavior in the solution vector for chemical concentration. Conservative criteria for nodal spacing for saturated flow can be used to set nodal spacing for unsaturated zone transport. When nodal spacing criteria are satisfied, for the same set of transport and boundary conditions, chemical concentration profiles calculated by the two numerical methods will be almost the same. A situation that is simulated very well with one-dimensional models, is the application of chemicals to land surfaces. To compare and contrast the characteristics of solutions given by the two numerical methods, moisture content, temperature and chemical concentration profiles for a 75-day period after application in the unsaturated zone are calculated for two representative types of organic chemicals. In the first, the chemical is very slowly degraded in the subsurface environment but strongly sorbed to soil surfaces. In the second, the chemical is rapidly degraded but weakly sorbed to soil surfaces. Because of differences in sorption coefficients and mechanisms of degradation, for the same set of hydrodynamic properties of the subsurface, the weakly sorbed chemical is more widely distributed throughout the unsaturated zone, whereas the strongly sorbed chemical stays very close to where it is put initially with little penetration into the subsurface. Satisfying nodal spacing criteria minimizes the impact of the method of approximation on the calculated solutions of the transport equations. For better model predictive performance, however, there are needs for more fundamental information on processes governing transport in the subsurface.     

Relative lipid content as the sole mechanistic determinant of the adipose tissue:blood partition coefficients of highly lipophilic organic chemicals

The adipose tissue:blood partition coefficient (PCat:b) refers to the ratio of chemical concentration or solubility in adipose tissue and blood. The solubility of a chemical in adipose tissue or whole blood is equal to the sum total of its solubility in lipid and water fractions of these matrices. For highly lipophilic organic chemicals (HLOCs, i.e., chemicals with log n-octanol:water partition coefficients (PCo:w) greater than four), their solubility in the water fractions of both tissue and blood is negligible, and therefore their solubility in lipid fractions of tissue and blood alone determines PCat:b. Since the numerical value representing chemical solubility in lipids is likely to be the same for both blood lipids and adipose tissue lipids, the PCat:b values should be hypothetically, equal to the ratio of lipid content of adipose tissue and blood. The objective of the present study was therefore to verify whether the PCat:bs of HLOCs (volatile organics, dioxins, PCBs, PBBs, DDT) are equal to the ratio of adipose tissue and blood lipid levels. The data on lipid content of rat and human blood and adipose tissues were obtained from the literature. The calculated tissue:blood lipid ratios were comparable to the human and rat PCat:b of volatile organic chemicals, dioxins, PCBs, PBBs and/or DDT obtained from the literature. These results then suggest that, regardless of the identity and PCo:w of HLOCs, their PCat:b is equal to the ratio of lipid in adipose tissues and blood.     

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.     

Dimension reduction and source identification for multispecies groundwater contamination

Assessment of chemical contamination at large industrial complexes with long and sometimes unknown histories of operation represents a challenging environmental problem. The spatial and temporal complexity of the contaminant may be due to changes in production processes, differences in the chemical transport, and the physical heterogeneity of the soil and aquifer materials. Traditional mapping techniques are of limited value for sites where dozens of chemicals with diverse transport characteristics may be scattered over large spatial areas without documentation of disposal histories. In this context, a site with a long and largely undocumented disposal history of shallow groundwater contamination is examined using principal component analysis (PCA). The dominant chemical groups and chemical "modes" at the site were identified. PCA results indicate that five primary and three transition chemical groups can be identified in the space of the first three eigenvectors of the correlation matrix, which account for 61% of the total variance of the data. These groups represent a significant reduction in the dimension of the original data (116 chemicals). It is shown that each group represents a class of chemicals with similar chemo-dynamic properties and/or environmental response. Finally, the groups are mapped back onto the site map to infer delineation of contaminant source areas for each class of compounds. The approach serves as a preliminary step in subsurface characterization, and a data reduction strategy for source identification, subsurface modeling and remediation planning.     

Microbial growth with vapor-phase substrate

Limited information exists on influences of the diffusive transport of volatile organic contaminants (VOC) on bacterial activity in the unsaturated zone of the terrestrial subsurface. Diffusion of VOC in the vapor-phase is much more efficient than in water and results in effective VOC transport and high bioavailability despite restricted mobility of bacteria in the vadose zone. Since many bacteria tend to accumulate at solid-water, solid-air and air-water interfaces, such phase boundaries are of a special interest for VOC-biodegradation. In an attempt to evaluate microbial activity toward air-borne substrates, this study investigated the spatio-temporal interplay between growth of Pseudomonas putida (NAH7) on vapor-phase naphthalene (NAPH) and its repercussion on vapor-phase NAPH concentrations. Our data demonstrate that growth rates of strain PpG7 were inversely correlated to the distance from the source of vapor-phase NAPH. Despite the high gas phase diffusivity of NAPH, microbial growth was absent at distances above 5 cm from the source when sufficient biomass was located in between. This indicates a high efficiency of suspended bacteria to acquire vapor-phase compounds and influence headspace concentration gradients at the centimeter-scale. It further suggests a crucial role of microorganisms as biofilters for gas-phase VOC emanating from contaminated groundwater or soil.     

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.     

A model of oscillatory transport in granular soils, with application to barometric pumping and earth tides

A simple algebraic model is proposed to estimate the transport of a volatile or soluble chemical caused by oscillatory flow of fluid in a porous medium. The model is applied to the barometric pumping of vapors in the vadose zone, and to the transport of dissolved species by earth tides in an aquifer. In the model, the fluid moves sinusoidally with time in the porosity of the soil. The chemical concentration in the mobile fluid is considered to equilibrate with the concentration in the surrounding matrix according to a characteristic time governed by diffusion, sorption, or other rate processes. The model provides a closed form solution, to which barometric pressure data are applied in an example of pore gas motion in the vadose zone. The model predicts that the additional diffusivity due barometric pumping in an unfractured vadose zone would be comparable to the diffusivity in stagnant pore gas if the equilibration time is 1 day or longer. Water motion due to the M2 lunar tide is examined as an example of oscillatory transport in an aquifer. It is shown that the tidal motion of the water in an aquifer might significantly increase the vertical diffusivity of dissolved species when compared to diffusion in an absolutely stagnant aquifer, but the hydrodynamic dispersivity due to tidal motion or gravitational flow would probably exceed the diffusivity due to oscillatory advection.     

太仓市饮用水水源污染现状和对策

根据太仓市饮用水地表水源和地下水的监测数据，分别采用单因子评价和综合评价方法，对饮用水源的水质进行评价。结果认为地表水水源已受到轻度污染，属Ⅲ类水；地下水的水质较差，已不适合于直接饮用。饮用水水源的主要污染物为COD、氨氮、挥发酚、硝酸盐氮和高锰酸盐指数。对饮用水水源的污染成因进行了全面分析，并从四个方面提出了水源安全保护对策：法律法规与行政手段、技术支撑、经济支持和宣传教育.     

State of the Art Report on Mathematical Methods for Groundwater Pollution Source Identification

The reliable assessment of hazards or risks arising from groundwater contamination problems and the design of efficient and effective techniques to mitigate these problems require the capability to predict the behavior of chemical contaminants in flowing water. Most attempts at quantifying contaminant transport have relied on a solution of some form of a well-known governing equation referred to as advection-dispersion-reaction equation. To choose an appropriate remediation strategy, knowledge of the contaminant release source and time release history becomes pertinent. As additional contaminated sites are being detected, it is almost impossible to perform exhaustive drilling, testing, and chemical fingerprint analysis every time. Moreover, chemical fingerprinting and site records are not sufficient to allow a unique solution for the timing of source releases. The purpose of this paper is to present and review mathematical methods that have been developed during the past 15 years to identify the contaminant source location and recover the time release history.     

State of the Art Report on Mathematical Methods for Groundwater Pollution Source Identification

The reliable assessment of hazards or risks arising from groundwater contamination problems and the design of efficient and effective techniques to mitigate these problems require the capability to predict the behavior of chemical contaminants in flowing water. Most attempts at quantifying contaminant transport have relied on a solution of some form of a well-known governing equation referred to as advection-dispersion-reaction equation. To choose an appropriate remediation strategy, knowledge of the contaminant release source and time release history becomes pertinent. As additional contaminated sites are being detected, it is almost impossible to perform exhaustive drilling, testing, and chemical fingerprint analysis every time. Moreover, chemical fingerprinting and site records are not sufficient to allow a unique solution for the timing of source releases. The purpose of this paper is to present and review mathematical methods that have been developed during the past 15 years to identify the contaminant source location and recover the time release history.     

Fingerprinting and Groundwater Model Application to Evaluate Hydraulic Barrier Efficiency (Italy)

Remediation actions at contaminated sites are based on multiple numerical model scenarios considering different parameter distributions, source positions and contaminant transport paths. In some cases the excess of scenarios is due to uncertainties in the conceptual model as a result of the spread of contamination through heterogeneities in the physical system. Reduction of project hypotheses and conceptual model uncertainty is therefore needed. This result can be achieved by coupling hydrogeological investigations with environmental forensic techniques, better localization of the source and understanding of contamination history. In this respect, in the present study, compositional fingerprinting and groundwater flow modeling were applied to a former oil storage facility where, even though a hydraulic barrier had been built to stop the hydrocarbon plume, the presence of some hydrocarbons was still found in downgradient monitoring wells. The final aim was to evaluate the efficacy of the hydraulic barrier and identify of the source of pollution. Fingerprinting results indicated pollution with a gasoline-diesel mixture much altered by water washing and/or biodegradation. Comparison of seven groundwater samples collected in wells and monitoring wells was performed by analyzing the volatile fraction (BTEX) and the total ion chromatogram (TIC), focusing attention on: n-alkanes (m/z 85), alkylcyclohexanes (m/z 83), isoprenoids (m/z 113), C4-alkylbenzenes (m/z 134), C3-C6 alkylbenzenes and polycyclic aromatic hydrocarbons (PAHs). The most probable scenario was then identified by combining the results of fingerprinting with different contaminant paths obtained using the numerical model.