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.     

Dense Nonaqueous Phase Liquid Tracer Tests: Experimental Results

Two dense nonaqueous phase liquid (DNAPL) tracer tests werecarried out in a shallow aquifer north of Fort Worth, TX. i-Propanolwas used as the nonpartitioning tracer; n-hexanol and n-octanol werethe partitioning tracers. Field data, mathematical modeling, theresults of column tests, and field tracer tests with NaCl were usedin designing the DNAPL tracer tests. The results indicated the presenceof DNAPL at both sites tested; semi-quantitative estimates of theamounts of DNAPL present were obtained by mathematical modeling.Interpretation was complicated by heterogeneity of the aquifer andmass transport effects.     

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.     

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.     

Matrix diffusion effects in the cleanup of heterogeneous aquifers

Simple mathematical models are developed to account for the rather slow mass transport of nonaqueous phase liquid (NAPL) into aqueous solution in groundwater during flushing operations. The models are based on the assumption that this bottleneck in the process is associated with diffusion in the aqueous phase in the porous medium from the location of the NAPL drops/ganglia in a region of relatively low permeability out into a region of substantially higher permeability, somewhat analogous to diffusion from a block of porous rock into a nearby fracture, where the fracture system overwhelmingly dominates the overall permeability. The models include batch flushing, flushing in a laboratory column, and a one-dimensional model for flushing by means of a single recovery well.     

Modelling Tracer Dispersion from Landfills

Several wind tunnel experiments of tracer dispersion from reduced-scale landfill models are presented in this paper. Different experimental set-ups, hot-wire anemometry, particle image velocimetry and tracer concentration measurements were used for the characterisation of flow and dispersion phenomena nearby the models. The main aim of these experiments is to build an extensive experimental data set useful for model validation purposes. To demonstrate the potentiality of the experimental data set, a validation exercise on several mathematical models was performed by means of a statistical technique. The experiments highlighted an increase in pollutant ground level concentrations immediately downwind from the landfill because of induced turbulence and mean flow deflection. This phenomenon turns out to be predominant for the dispersion process. Tests with a different set-up showed an important dependence of the dispersion phenomena from the landfill height and highlighted how complex orographic conditions downwind of the landfill do not affect significantly the dispersion behaviour. Validation exercises were useful for model calibration, improving code reliability, as well as evaluating performances. The Van Ulden model proved to give the most encouraging results.     

Modelling the Removal of Gaseous Pollutants and Particulate Matters from the Atmosphere of a City by Rain: Effect of Cloud Density

In this paper, an original nonlinear mathematical model for the removal of gaseous pollutants and particulate matters from the atmosphere of an industrial city by rain is proposed and analyzed. It is assumed that five interacting phases in the atmosphere of the city exist, i.e., cloud droplets phase, raindrops phase, gaseous pollutants phase, particulate matters phase, and the phase of absorbed gaseous pollutants in raindrops. It is assumed further that these phases undergo nonlinear interactions in the atmosphere, while gaseous pollutant interacts with cloud droplets as well as with raindrops but particulate matters interact only with raindrops. The gravitational settling and reversible reaction processes have also been considered appropriately in the model. By analyzing the model, it is shown that both the gaseous pollutants and particulate matters may be removed from the atmosphere under certain conditions, provided the rates of formation of cloud droplets and raindrops are sufficiently large. It is noted that under unfavorable atmospheric conditions, rain does not occur and pollutants are not removed from the atmosphere.     

Soil Gas Volatile Organic Compound Concentration Contours for Locating Vadose Zone Nonaqueous Phase Liquid Contamination

Diffusion of VOC from cylindrical vadose zone domains contaminatedwith distributed nonaqueous phase liquid is examined in the steadystate approximation. The effects of first-order biodegradation and ofan extended underlying pool of LNAPL floating on the water table belowthe cylindrical domain are explored by means of an orthogonal functionsapproach. The distribution of VOC in the vadose zone above a floatingcircular LNAPL pool of finite size is explored by a numerical method.The results provide information useful in estimating the spacing anddepth at which soil gas samples should be taken in order to detect thepresence of such source areas. Comparison of model results with soilgas VOC measurements at various depths also provides insight into theextent to which natural biodegradation of the VOCs is taking place.     

A field-based spectrophotometric flow-injection system for automatic determination of chloride in soil water

The use of chloride as a tracer for soil water investigations is discussed. Limitations with laboratory based soil core and field based sampling are considered with respect to the poor suitability of the data for rigorous assessment of mechanistic models. Investigation of water movement in soil has been restricted by limitations in spatial and temporal sampling. Fine resolution sampling generates large numbers of samples which cause problems with post sampling laboratory analysis. This paper describes a field-based system for the analysis of chloride in soil water. There are three component parts to the system, (i) a custom sampling sub-system comprising of ceramic cup suction samplers and sample traps, (ii) a sample routing sub-system to channel sample to (iii) a sample analysis sub-system utilizing a flow injection method for sample analysis using a custom built photo-diode detector. The three sub-systems were controlled by a suitably equipped personal computer. A calibration procedure is described with a third order polynomial equation derived to convert millivolt response from the detector into chloride concentration. Field and laboratory data from a tracer experiment are presented and discussed, and it is concluded that the system is well suited to field-based applications. Finally it is noted that the photo-detector is suitable for colourimetric analysis of any tracer with suitable chemical determination.     

Some Advances in Fluorometric Techniques for Water Tracing

A common technique for ground water tracing uses continuous or discrete analysis of fluorescent tracer dyes to produce tracer breakthrough curves which can be analysed to determine ground water trajectory, velocity and dispersivity. Some fluorescent dyes are excellent tracers, but there remain significant constraints in fluorometry with respect to installation, control and data acquisition using standard filter fluorometers as well as with general analytical protocols. This paper identifies some of the constraints associated with the widely used Turner Designs Model 10 Series filter fluorometer and technical and operational solutions which can significantly improve the precision, accuracy and time resolution of tracer data.     

Practical considerations optically sensing rhodamine WT in water impacted by municipal biosolids

Rhodamine WT (RWT) is an adsorptive flourescent dye tracer that is used in hydrological and hydrogeological studies. Municipal biosolids (sewage) are rich in organic matter and have a variety of chemical constituents that can interact to confound optical sensing of RWT florescence in water (e.g., quenching, interference, adsorption). Laboratory studies were conducted to evaluate optical sensing constraints associated with quantifying known RWT concentrations in a suite of RWT-spiked distilled water/liquid municipal biosolid (LMB) mixes. RWT flourescence decreased with an increase in LMB total suspended solids (TSS) in decay function form (R ²?=?0.98). A method was then described to correct the undersensed RWT readings based on knowledge of TSS and/or turbidity. This study also found that, for samples agitated by stirring, RWT readings increased in logarithmic form over time. In addition, sample agitation augmented the undersensing of known RWT concentrations, but when agitation ceased, optical readings immediately approached more closely the known RWT values. Studies that use RWT as a tracer to assess the fate and transport of biosolid impacted water in hydrological environments should be aware of some of the optical sensing limitations identified here.     

Beach geomorphic factors for the persistence of subsurface oil from the Exxon Valdez spill in Alaska

Oil from the 1989 Exxon Valdez oil spill persists in some of the Prince William Sound (Alaska) beaches and continues to be a potential threat to the fauna. This paper reports a field investigation during the summer of 2008 of groundwater flow and solute transport in a tidal gravel beach in Smith Island, Prince William Sound. The beach contains oil on one side, the left side (facing landward). Field measurements of water table, salinity, and tracer (lithium) concentration were obtained for an approximate duration of 64 h for two transects, the oiled transect and a clean transect (the right transect). It was found that the hydraulic conductivity and the fresh groundwater recharge into the two transects were similar. It was also found that the beach slope of the mid to high tidal zone along the oiled (left) transect was ~7.4% which is considerably smaller than that of the clean (right) transect (~11.8%). This suggests a higher flushing/replenishing of the right transect with nutrients and/or oxygen, which would have enhanced biodegradation of oil on the right transect if that oil was not washed by waves. We also found that the degree of oiling at each location was inversely dependent on the armoring of the beach surface with clasts and boulders. The applied tracer concentration at the left transect was less than 2% of the source or close to the background level at all locations except a seaward well closest to the applied location, indicating that the tracer applied was diluted or washed out from the beach during the application. Thus, in situations where oil biodegradation is limited by the availability of nutrients and/or dissolved oxygen, applying the chemicals on the beach surface would most likely not enhance oil biodegradation as the applied chemicals would be greatly diluted prior to reaching the oil. Thus, deep injection of nutrients and/or dissolved oxygen is probably the only option for enhancing oil biodegradation.     

Investigation of Building - Influenced Atmospheric Dispersion Using a Dual Source Technique

Dispersion of atmospheric contaminants in the vicinity of an isolated cubical model building was investigated in the field. A dual source/receptor technique was used in the experiments, which was proved to be very useful for the investigation of pollution dispersion. This experimental technique involved the simultaneous release of two different tracer gases from two different point sources, and the deployment of a FID (Flame Ionization Detector) co-located with a UVIC®(Ultra-Violet Ion Collector) detector. Both mean concentrations and concentration fluctuation statistics were examined. In this paper concentration fluctuation statistics are presented. The effect of the upwind source location on intermittency values and on the cumulative density function (cdf) is examined. The exact location of a source placed upwind of an obstacle has a very significant and complex effect on both mean concentrations and concentration fluctuations. As the lateral or vertical displacement between the two sources is increased, cross-correlation values between data taken simultaneously by two co-located detectors decrease rapidly.     

Estimating overall persistence and long-range transport potential of persistent organic pollutants: a comparison of seven multimedia mass balance models and atmospheric transport models

Two different approaches to modeling the environmental fate of organic chemicals have been developed in recent years. The first approach is applied in multimedia box models, calculating average concentrations in homogeneous boxes which represent the different environmental media, based on intermedia partitioning, transport, and degradation processes. In the second approach, used in atmospheric transport models, the spatially and temporally variable atmospheric dynamics form the basis for calculating the environmental distribution of chemicals, from which also exchange processes to other environmental media are modeled. The main goal of the present study was to investigate if the multimedia mass balance models CliMoChem, SimpleBox, EVn-BETR, G-CIEMS, OECD Tool and the atmospheric transport models MSCE-POP and ADEPT predict the same rankings of the overall persistence (P(ov)) and long-range transport potential (LRTP) of POPs, and to explain differences and similarities between the rankings by the mass distributions and inter-compartment mass flows. The study was performed for a group of 14 reference chemicals. For P(ov), the models yield consistent results, owing to the large influence of phase partitioning parameters and degradation rate constants, which are used similarly by all models. Concerning LRTP, there are larger differences between the models than for P(ov), due to different LRTP calculation methods and spatial model resolutions. Between atmospheric transport models and multimedia fate models, no large differences in mass distributions and inter-compartment flows can be recognized. Deviations in mass flows are mainly caused by the geometrical design of the models.     

An Experimental Methodology for Monitoring Contaminant Transport Through Geotechnical Centrifuge Models

In this paper, an attempt has been made to highlight an experimental methodology for monitoring contaminant transport through locally available silty soil and commercially available clay in geotechnical centrifuge models, for different compaction states. Use of multiple depth sensors to determine depth distribution of sodium chloride in the soil column has been detailed. The obtained results have been compared with argentometric method. To validate the centrifuge modelling, modelling of models has been used. The test setup developed can simulate contaminant transport mechanisms through the soil mass, which is approximately 10 m deep, over a period of 600 days. R _e and P _e are found to be N times higher in the centrifuge models. These numbers are found to be several orders less than unity. This indicates that laminar flow prevails and the dominating Cl⁻ transport mechanism in centrifuge is diffusion. The study also highlights the fact that the geotechnical centrifuge modelling can be used as a viable alternative to field scale experimentation.     

Ultrasound-assisted ionic liquid-based microextraction combined with least squares support vector machines regression for the simultaneous determination of aluminum,gallium, and indium in water and coal samples

A new simple and rapid ultrasound-assisted ionic liquid-based microextraction method was applied to preconcentrate aluminum(III), gallium(III), and indium(III) ions from water samples as a prior step to their simultaneous spectrophotometric determination using least squares support vector machines regression. In the novel procedure, 1-hexyl-3-methylimidazolium hexafluorophosphate [C₆MIM][PF₆] was dispersed into the aqueous sample solution as fine droplets by ultrasonication, and the analytes were extracted into the ionic liquid phase after complexation with 1,2,5,8-tetrahydroxy anthraquinone (quinalizarine). After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom glass centrifuge tube. The detection limits for Al(III), Ga(III), and In(III) were 1.70, 2.02, and 2.06 ng mL⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of ten replicates, was below 3.2% for all elements. The method was successfully applied for the determination of Al(III), Ga(III), and In(III) in real samples.     

Atrazine Transport Within a Coastal Zone in Southeastern Puerto Rico: a Sensitivity Analysis of an Agricultural Field Model and Riparian Zone Management Model

Agrichemical runoff from farmland may adversely impact coastal water quality. Two models, the Agricultural Policy/Environmental eXtender (APEX) and the Riparian Ecosystem Management Model (REMM), were used to evaluate the movement of the herbicide atrazine to the Jobos Bay National Estuarine Research Reserve from adjacent fields. The reserve is located on Puerto Rico’s southeast coast. Edge-of-field atrazine outputs simulated with the APEX were routed through a grass-forest buffer using the REMM. Atrazine DT₅₀ (half-life) values measured in both field and buffer soils indicated that accelerated degradation conditions had developed in the field soil due to repeated atrazine application. APEX simulations examined both the measured field and buffer soil atrazine DT₅₀ and the model’s default value. The use of the measured field soil atrazine degradation rate in the APEX resulted in 33 % lower atrazine transport from the field. REMM simulations indicated that the buffer system had the potential to reduce dissolved atrazine transport in surface runoff by 77 % during non-tropical storm events by increasing infiltration, slowing transport, and increasing time for pesticide degradation. During a large runoff event due to a tropical storm that occurred close to the time of an atrazine application, the REMM simulated only a 37 % reduction in atrazine transport. The results indicate that large storm events soon after herbicide application likely dominate herbicide transport to coastal waters in the region. These results agree with water quality measurements in the reserve. This study demonstrated the sensitivity of these models to variations in DT₅₀ values in evaluating atrazine fate and transport in the region and emphasizes that the use of measured DT₅₀ values can improve model accuracy.     

大气颗粒物源解析受体模型应用研究及发展现状

通过大量文献资料调研对化学质量平衡模型、二重源解析技术、主因子分析、正矩阵因子分析法等目前应用较广泛的受体模型方法的原理、优缺点和应用现状进行了比较分析,对单颗粒源解析方法、有机物示踪技术和扩散与受体模型联用技术等受体模型新技术方法进行了评述。