Cleanup of fractured rock aquifers. II. Effects of matrix diffusion and nonaqueous phase liquid

Model calculations are used to explore the effects of the kinetics of diffusion of dissolved organic compounds into and out of low-permeability porous materials and of the rate of solution of nonaqueous phase liquid (NAPL) droplets (into the aqueous phase) on the rate of cleanup of contaminated aquifers. Two models are presented: (1) the flushing of organic compounds initially distributed as NAPL droplets in a fracture in a porous rock aquifer, and (2) the removal of organic compounds initially present as NAPL in an aquifer containing low-permeability porous clay lenses. NAPL droplet size is found to be of much less importance than the spacing of the fractures in the porous rock in the first model or the thickness of the clay lenses in the second.     

Migration of pollutants in groundwater. V. Modelling the removal of DNAPL droplets by flushing

Mathematical models are developed for the flushing of droplets of dense nonaqueous phase liquids (DNAPLs) distributed in aquifers. The kinetics of the diffusion of dissolved volatile organic compound (VOC) from the droplets into the moving liquid is included in the models. Models are developed for the flushing of DNAPL droplets in lab columns, in aquifers with a one-dimensional radial flow field and in quiescent aquifers in which a single well screened at the bottom is used to bring about the flushing. Some representative results are given.     

Mathematical Modeling of Column and Field Dense Nonaqueous Phase Liquid Tracer Tests

Mathematical models for the simulation of dense nonaqueous phase liquid tracer tests (DTTs) in laboratory columns and in the field are developed and examined. The DTT technique is a means of estimating the quantity of dense nonaqueous phase liquid (DNAPL) in a domain of interest in an aquifer. The two-dimensional field DTT model uses the Method of Principal Directions and an asymmetrical upwind algorithm for describing advective transport. Both models include diffusion transport of tracer into and from low-permeability porous structures such as clay lenses, as well as the mass transport kinetics of partitioning tracer to and from the DNAPL droplets. The dependence of the effluent tracer concentration curves on the parameters of the models is explored, and conclusions are drawn regarding the applicability of, and several possible problems with, the DTT technique. Model results indicate that the DTT performs well at locating distributed droplets of DNAPL, but is unlikely to be useful in the assessment of pooled DNAPL.     

Surfactant dissolution and mobilization of LNAPL contaminants in aquifers

Improper disposal, accidental spills and leaks of non-aqueousphase liquids (NAPL) such as gasoline, fuel oil and creosote result in long-term persistent sources of groundwater pollution.Column and 2-D tanks experiments were conducted to evaluate the use of surfactant-enhanced recovery of light non-aqueous phase liquids (LNAPL) in groundwater aquifers. These experiments focused on the use of surfactants to promote dissolution and mobilization in addition to evaluating the increase of aqueous phase permeability as residual NAPL is recovered. Further experiments are presented that show the innovative use of surfactants during primary pumping to recover free product canpotentially increase the amount of free product recovered, canpotentially reduce the amount of residual NAPL remaining afterprimary pumping and performs better than the use of surfactantsto mobilize trapped residual NAPL.     

Migration of pollutants in groundwater. VI. Flushing of DNAPL droplets/ganglia

Models for describing the flushing of DNAPL from contaminated aquifers are developed, and the dependence of the calculated cleanup times on the model parameters is explored. Diffusion transport from isolated DNAPL droplets, from low-permeability porous spherical domains containing distributed DNAPL droplets, and from low-permeability porous planar lamellae containing distributed DNAPL is analyzed, and the resulting expressions then coupled with the equations for advective transport of dissolved VOC by means of natural uniform flow and a system of injection and recovery wells generating a two-dimensional flow field. The models are readily run on currently available microcomputers. The results of computations with the models are consistent with the severe tailing and slow rates of remediation which are generally observed when DNAPLs are removed by flushing.     

Experimental Methodology to Assess Contaminant Diffusion in Rock Mass

Monitoring changes in electrical conductivity (EC) of aqueous phase, due to contaminant diffusion through porous media, is one of the techniques followed by researchers to understand the migration mechanism. However, the contaminant diffusion in the rock mass is a slow process and hence detecting small changes in conductivity with the help of conventional laboratory conductivity meters is quite difficult. With this in view, an experimental methodology to monitor diffusion of contaminant(s) through the intact and fractured rock mass, with the help of a USDTS (Ultra-Sensitive Devices and Technical Services) conductivity meter, has been developed. Results have been validated with those obtained from the ion chromatograph (IC) technique and a good agreement has been noted. The study demonstrates usefulness of the proposed methodology for online monitoring of contaminant migration through the porous media.     

Assessment of cyclodextrin-enhanced extraction of crude oil from contaminated porous media

The purpose of this study was to evaluate the effects of cyclodextrin (CD) on the extraction of Macondo well oil from contaminated porous media over a range of hydroxypropyl-β-CD (HPβCD) concentrations. To our knowledge, this is the first dataset on this type of CD yet assembled for an actual crude oil. The results showed that HPβCD can significantly increase oil extraction efficiency, demonstrated by increasing concentrations of all tested normal alkanes (nC(15)-nC(35)) and polyaromatic hydrocarbons (PAHs) in the aqueous phase with increasing CD concentration. A linear relationship between the extraction enhancement effect and CD concentration were verified experimentally and high correlation coefficients for total PAHs (R(2) = 0.82) and alkanes (R(2) = 0.99) were determined. For a 20% CD solution, 3.13 wt% of alkanes and 32.12 wt% of total PAHs were extracted to the aqueous phase, which was significantly more than what was extracted with water only (0.04% and 0.21% for alkanes and PAHs, respectively). This result shows that the remediation of oil contaminated media can be significantly enhanced through the use of HPβCD solutions in flushing or pump and treat operations to remove sorbed oil. The CD extraction enhancement effect decreases with increasing n-alkane chain length for the carbon number range tested. CD significantly enhanced PAH extraction from sand and the enhancement effect increased in the order of parent compounds < C-1 substituted < C-2 substituted < C-3 substituted for most PAHs tested. This study provides important information to assess the feasibility of using CD as a near-shore agent to enhance the cleanup of oil contaminated porous media.     

Solid-phase extraction using hierarchical organosilicates for enhanced detection of nitroenergetic targets

A novel porous organosilicate material was evaluated for application as a solid phase extraction sorbent for preconcentration of nitroenergetic targets from aqueous solution prior to HPLC analysis. The performance of the sorbent in spiked deionized water, groundwater, and surface water was evaluated. Targets considered included 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, RDX, HMX, and nitroglycerin. The sorbent was shown to provide improved performance over Sep-Pak RDX. The impact of complex matrices on target preconcentration by the sorbent was also found to be less dramatic than that observed for LiChrolut EN. The impact of changes in pH on target preconcentration was considered. Aqueous soil extracts generated from samples collected at sites of ordnance testing were also used to evaluate the materials. The results presented here demonstrate the potential of this novel sorbent for application as a solid phase extraction material for the preconcentration of nitroenergetic targets from aqueous solutions.     

Soil heterogeneity effects on acid flushing of lead-contaminated soil

A compact model for evaluation of acid flushing of heavy-metal-contaminated soil in a small-scale on-site treatment plant is proposed. The model assumes that the soil was re-packed in a container after excavation resulting in a soil structure with heterogeneous and random physical and chemical properties. To evaluate the effects of heterogeneity on the efficiency of contaminant removal by acid flushing, a numerical analysis of lead transport in the heterogeneous soil medium was performed. The model examines cation exchange and surface complexation reactions involving three cations (Ca, Pb, and H) and one anion (Cl) in both dissolved and exchangeable forms, two Pb surface complexes (SOPbCl and SOPbOH), and one Cl surface complex (SOH₂Cl). The transport of these species during flushing with acid in a synthetically generated two-dimensional heterogeneous soil was simulated in the model. Results indicated that the flushing fluid preferentially followed pathways with large permeability. The heterogeneous cation exchange capacity (CEC) distribution and surface complexation sites had a significant effect on the transport of dissolved species. Because the CEC was set to a relatively low value, Pb was adsorbed mainly as surface complexes (SOPbCl and SOPbOH). Simulation results suggest that blocks of low hydraulic conductivity located in the upper part of the model domain greatly impede solute transport. Ponding conditions did not significantly affect the efficiency of decontamination. The model and its results are useful in the design of small-scale treatment plants for acid flushing.     

Migration of pollutants in groundwater. IV. Modeling of the pumping of contaminants from fractured bedrock

The removal of soluble contaminants from fractured porous bedrock by means of a recovery well is modeled by means of a lumped parameter approach. The diffusion of contaminant from immobile liquid within the pores of the fractured rock into the mobile liquid in the interstices is handled by means of a time constant the estimation of which is described.     

Performance evaluation of 1-D numerical model HEC-RAS towards modeling sediment depositions and sediment flushing operations for the reservoirs

Sediment inflow to the reservoir is a key factor to calculate life of the reservoir. Flushing is a very useful technique in order to enhance the life of reservoir. From the literature review, 14 reservoirs were considered where flushing has already been practiced and only 6 reservoirs were found successful in flushing. The others were found partially flushed. In this research, data of three successfully flushed reservoirs namely Baira reservoir (India), Gebidem reservoir (Switzerland), and Gmund reservoir (Austria) were used to run 1-D numerical model HEC-RAS. In the first phase, the longitudinal profiles of delta were modeled and calibrated with observed sediment depositions. In the presence of available data of discharges and respective reservoir levels, the modeled deltas were used for flushing the deltas. With the help of modeled delta and corresponding flushing discharges, sediment deposition and flushing durations were computed. The simulated flushed durations were 31, 102, and 180 h for Baira, Gebidem, and Gmund reservoirs, respectively. The simulated flushed durations were found close to observed durations. Hence, the use of 1-D numerical model HEC-RAS is encouraged for modeling of sediment deposits and flushing operations.     

污染场地土壤通用评估基准建立的理论和常用模型

污染场地土壤通用评估基准的建立与每个国家的经济水准及社会发展紧密相关.从国际相关领域的发展趋势来看,场地基准的建立基于风险基础之上.我国正在颁布污染场地风险评估技术导则(C-RAG),表明我国已选择风险基础上的污染场地管理模式.文章回顾了污染场地土壤通用评估基准建立的理论、方法及通用模型,并推荐污染场地评估的模型框架,...     

Joint Impact of Scaling and Hysteresis on NAPL Flow Simulation

The hysteresis of capillary pressure versus saturation (P–S) relation is an important constitutive relation in multiphase flow, since the P–S relation is widely used to predict P–S relations in the simulation of the non-aqueous phase liquids (NAPLs). This work examined the performance of the scaling rule on predicting the P–S relationship and then studied the joint impact of the scaling and hysteresis on the multiphase NAPL flow simulation. Various experimental P–S values of distinct fluid pairs were compared with the scaled P–S curves using the scaling rule. The comparison indicated that the prediction of P–S is more accurate when the water–air P–S curve is used to scale other P–S curves. The joint impact of the scaling and hysteresis on the NAPLs flow simulation was then investigated by numerical simulation studies. The NAPL simulator was used to simulate the outcome of several scenarios based on a system with water–NAPL–air in a hypothetical sand tank. For both gasoline and trichloroethylene, the difference of the injected NAPL volume between no hysteretic and hysteretic simulations over a given time period was the smallest when the water–air P–S curve was used to scale other P–S curves. Simulation results of this study are valuable references for predicting the distribution of NAPLs.     

Quantification of Water, Salt and Nutrient Exchange Processes at the Mouth of A mediterranean Coastal Lagoon

Vassova lagoon is a typical Mediterranean (small, shallow, micro-tidal, well-mixed) coastal lagoon, receiving limited seasonal freshwater inflows from direct precipitation and underground seepage. An intensive study was carried out in order to quantify the mechanisms responsible for the intra-tidal and residual transport of water, salt, nutrients and chlorophyll at the mouth of this lagoon and to assess the lagoon's flushing behavior. Results indicated that although the system is micro-tidal, tidal effects appeared to be the dominant factor for the longitudinal distribution of physical and chemical parameters, while the associated residual flow is also important and serves as a baseline measure of overall circulation. However, analysis of the net longitudinal currents and fluxes of water, salt and nutrients revealed the importance of non-tidal effects (wind effect and precipitation incidents) in the mean tidal transport. It is shown that the Eulerian residual currents transported water and its properties inwards under southern winds, while a seaward transport was induced during precipitation incidents and northern winds. The Stokes drift effect was found an order of magnitude lower than the Eulerian current, directed towards the lagoon, proving the partially-progressive nature of the tide. Nutrients and chlorophyll-α loads are exported from the lagoon to the open sea during the ebb phase of the autumn and winter tidal cycles, associated with the inflow of nutrient-rich freshwater, seeped through the surrounding drainage canal. The reverse transport occurs in spring and early summer, when nutrients enter the lagoon during the flood tidal phase, from the nutrient-rich upper layer of the stratified adjacent sea. Application of a tidal prism model shows that Vassova lagoon has a mean flushing time of 7.5 days, ranging between 4 to 18 days, affected inversely by the tidal oscillation.     

Study on gas diffusion emitted from different height of point source

The flow and dispersion of stack-gas emitted from different elevated point source around flow obstacles in an urban environment have been investigated, using computational fluid dynamics models (CFD). The results were compared with the experimental results obtained from the diffusion wind tunnel under different conditions of thermal stability (stable, neutral or unstable). The flow and dispersion fields in the boundary layer in an urban environment were examined with different flow obstacles. Gaseous pollutant was discharged in the simulated boundary layer over the flat area. The CFD models used for the simulation were based on the steady-state Reynolds-Average Navier-Stoke equations (RANS) with kappa-epsilon turbulence models; standard kappa-epsilon and RNG kappa-epsilon models. The flow and dispersion data measured in the wind tunnel experiments were compared with the results of the CFD models in order to evaluate the prediction accuracy of the pollutant dispersion. The results of the CFD models showed good agreement with the results of the wind tunnel experiments. The results indicate that the turbulent velocity is reduced by the obstacles models. The maximum dispersion appears around the wake region of the obstacles.     

Modelling the Competitive Sorption Process of Multiple Solutes During their Transport in Porous Media

A general mathematical model to solve the advection–dispersion transport equation for multiple solutes was developed, where the dual porosity mobile–immobile mass transfer, the two-site non-equilibrium model and first-order transformation reactions were included. The two-site model was expressed with an equilibrium sorption term and a kinetic term. One of three kinetic models could be used: the non-linear, the bilinear and the pore diffusion model. The traditional Freundlich or Langmuir isotherms were employed to simulate no-interaction between the solutes, but with the extended Freundlich or extended Langmuir isotherms, a competitive sorption could be simulated. The transport equation was solved with the Moving Concentration Slope method. The mathematical model was tested and further simplified by using real data from soil column experiments, with 1,2-cis-dichloroethene and trichloroethene as model contaminants and silica gel and real soil samples as porous medium.     

Cleanup of fractured rock aquifers: Implications of matrix diffusion

As contamination moves through a fractured rock aquifer, it tends to diffuse from the flowing fracture water into the rock's essentially stagnant pore water. This process tends both to retard a contamination plume's advance through a fractured rock aquifer and to substantially increase the difficulty of purging contamination from the aquifer. A mathematical model has been developed to evaluate the potential impact of this phenomenon upon water quality restoration in fractured rock aquifers. The numerical modeling reveals that cleanup of fractured rock aquifers will, in many cases, require many decades, even centuries, to achieve, particularly where substantial improvements in water quality are sought. The parameters which most strongly govern the degree to which matrix diffusion prolongs the aquifer restoration process are the rock's matrix porosity, fracture spacing, and matrix diffusivity, the chemical identity of the contaminant(s), and the length of time the aquifer has been contaminated.Since sedimentary rocks tend to have both relatively high matrix porosities and matrix diffusivities, it can be particularly difficult to purge contamination from sedimentary rock aquifers. Crystalline rocks, in contrast, typically have lower matrix porosities and matrix diffusivities, and therefore undergo more rapid cleanup. However, even in crystalline rocks, attainment of very high degrees of water quality improvement may be problematic. Numerical modeling also indicates that conventional groundwater pump and treat programs are not likely to be very effective in speeding up aquifer restoration if the rate limiting step in the process is diffusion of contaminants from the rock matrix.     

Inter- and Intra-Annual Chemical Variability During the ice-Free Season in Lakes with Different Flushing Rates and Acid Deposition Histories

Quantifying chemical variability in different lake types is important for the assessment of both chemical and biological responses to environmental change. For monitoring programs that emphasize a large number of lakes at the expense of frequent samples, high variability may influence how representative single samples are of the average conditions of individual lakes. Intensive temporal data from long-term research sites provide a unique opportunity to assess chemical variability in lakes with different characteristics. We compared the intra- and inter-annual variability of four acidification related variables (Gran alkalinity, pH, sulphate concentration, and total base cation concentration) in four lakes with different flushing rates and acid deposition histories. Variability was highest in lakes with high flushing rates and was not influenced by historic acid deposition in our study lakes. This has implications for the amount of effort required in monitoring programs. Lakes with high flushing rates will require more frequent sampling intervals than lakes with low flushing rates. Consideration of specific lake types should be included in the design of monitoring programs.     

Preferential adsorption of fluorescing fulvic and humic acid components on activated carbon using flow field-flow fractionation analysis

Activated carbon treatment of drinking water is used to remove natural organic matter (NOM) precursors that lead to the formation of disinfection byproducts. The innate hydrophobic nature and macromolecular size of NOM render it amenable to sorption by activated carbon. Batch equilibrium and minicolumn breakthrough adsorption studies were performed using granular activated carbon to treat NOM-contaminated water. Ultraviolet (UV) absorption spectroscopy and flow field-flow fractionation analysis using tandem diode-array and fluorescence detectors were used to monitor the activated carbon sorption of NOM. Using these techniques, it was possible to study activated carbon adsorption properties of UV absorbing, fluorescing and nonfluorescing, polyelectrolytic macromolecules fractionated from the total macromolecular and nonmacromolecular composition of NOM. Adsorption isotherms were constructed at pH 6 and pH 9. Data were described by the traditional and modified Freundlich models. Activated carbon capacity and adsorbability were compared among fractionated molecular subsets of fulvic and humic acids. Preferential adsorption (or adsorptive fractionation) of polyelectrolytic, fluorescing fulvic and humic macromolecules on activated carbon was observed. The significance of observing preferential adsorption on activated carbon of fluorescing macromolecular components relative to nonfluorescing components is that this phenomenon changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the composition that existed in the aqueous phase prior to adsorption. Likewise, it changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the adsorbed phase. This research increases our understanding of NOM interactions with activated carbon which may lead to improved methods of potable water production.