A semi-analytical solution based on a numerical solution of the solute transport of a conservative and nonreactive tracer

In the evaluation of potential risk from ingestion of groundwater near an impacted site, numerical simulation of fate and transport processes of chemicals of concern is often required. If there is potential concern about multiple chemicals, numerical simulation of each chemical separately is often needed. In this paper, a semi-analytical solution is presented based on a numerical solution of the transport of a conservative and nonreactive tracer. When multiple chemicals undergoing sorption and first-order degradation need to be modeled, we can avoid performing individual numerical simulations for each chemical by applying the semi-analytical solution. Numerical test runs were conducted to verify the semi-analytical solution; simulation results reveal that the concentrations derived from the semi-analytical solution are identical to those derived from the individual numerical fate and transport model simulations. The semi-analytical solution requires steady-state flow conditions, no continuing contaminant source, and similar initial source concentration distributions.     

Uptake of Dissolved and Oil Phase Organic Chemicals by Bacteria

Hydrophobic organic chemicals (HOCs) discharged into soil and ground water will partition into gaseous, aqueous, oil, and sorbed phases. Knowledge of how bacteria assimilate HOCs is important to individuals involved in evaluating intrinsic, or engineered, bioremediation. The majority of bacteria isolated from the subsurface are gram-negative. The outer membrane of gram-negative organisms acts as a selective barrier to many solutes, including hydrophobic chemicals. Thus, diffusional transport of a hydrophobic solute through the outer membrane may be the rate-limiting step in biodegradation. Bacteria may also produce biosurfactants that can facilitate cell-oil contact or assist solubilization of oil and sorbed phases.     

The influence of biogeochemical conditions and level of model complexity when simulating cometabolic biodegradation in sorbent-water systems

Eighteen models with different levels of complexity for representing sorption, mass transfer, and biodegradation are used to simulate the biodegradation of toluene (primary substrate) and TCE (cometabolic substrate). The simulations are conducted for hypothetical completely mixed systems of various scenarios with regard to sorbent, microbial composition, and solute concentrations. The purpose of the suite of simulations is to investigate the sensitivity of different modeling approaches in simulating the bio-attenuation of co-existing solutes in sorbent-water systems. The sensitivity of results to the modeling approach depends on the biogeochemical conditions of the system. For example, the results are insensitive to the type of sorption model in systems with low sorption strength and slow biodegradation rates, and insensitive to the biodegradation rate model if mass transfer controlled. Differences among model results are generally greater when evaluated in terms of total mass removal rather than aqueous phase concentration reduction. The fate of the cometabolite is more sensitive to the proper consideration of co-solute effects than is the fate of the primary substrate. For a given system, graphical comparison of a characteristic mass transfer rate coefficient (α_mt) versus a characteristic biodegradation rate coefficient (α_bio) provides an indication of how sensitivity to the different processes may be expected to change with time and can guide the selection of an appropriate level of model complexity.     

Transport and Biological Fate of Toluene in Low-Permeability Soils

The effect of simultaneous sorption, diffusion, and biodegradation on the fate and transport of toluene in low-permeability soil formations was examined. A transport model accounting for vapor and liquid sorption, vapor diffusions, and first-order biodegradation was developed to describe the movement of volatile solute in unsaturated soils. Modeling studies were followed with laboratory batch and column studies on fine-grained soil samples obtained from a gasoline-contaminated site. Batch experiments yielded the sorption and diffusion coefficients for generating theoretical solute transport profiles. Column studies were conducted to examine toluene sorption, diffusion, and biodegradation under aerobic and denitrifying conditions. Results from the column studies indicated that vapor sorption onto the soil was minimal due to the high moisture content of the soil. Comparison of model predictions with experimental results indicated that the SASK model, which is based on the resistivity theory, provided a more accurate prediction of the vapor phase tortuosity than the frequently used Millington-Quirk equation. Laboratory results of toluene concentration profiles matched well with the model predictions and yielded degradation rates comparable to those obtained in the field. Column studies, examining toluene biodegradation under aerobic and denitrifying conditions in low-permeability soils, indicated that the presence of excess nitrate in aerobic environments yielded higher solute degradation rates than those observed under exclusively aerobic systems.     

Effects of Process Control Changes on Aquifer Oxygenation Rates During In Situ Air Sparging in Homogeneous Aquifers

In situ air sparging is used to remediate petroleum fuels and chlorinated solvents present as submerged contaminant source /ones and dissolved contaminant plumes, or to provide barriers to dissolved contaminant plume migration. Contaminant removal occurs through a combination of volatilization and aerobic biodegradation: thus, the performance at any given site depends on the contaminant and oxygen mass transfer rates induced by the air injection. It has been hypothesized that these rates are sensitive to changes in process flow conditions and site lithology, but no data is available to identify trends or the magnitude of the changes. In this work, oxygenation rates were measured for a range of air injection rates, ground water flow rates, and pulsing frequencies using a laboratory-scale two-dimensional physical model constructed to simulate a homogeneous hydrogeologic setting. Experiments were conducted with water having low chemical and biochemical oxygen demand. Results suggest the following: that there is an optimum air injection rate: advective How of ground water can be a significant factor when ground water velocities are > 0.3 m/d: and pulsing the air injection had little effect on the oxygenation rate relative lo the continuous air injection case.     

The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

A Practical Approach to Evaluating Natural Attenuation of Contaminants in Ground Water

The extent of natural attenuation is an important consideration in determining the most appropriate corrective action at sites where ground water quality has been impacted by releases of petroleum hydrocarbons or other chemicals. The objective of this study was to develop a practical approach that would evaluate natural attenuation based on easily obtained field data and field tested indicators of natural attenuation. The primary indicators that can he used to evaluate natural attenuation include plume characteristics and dissolved oxygen levels in ground water. Case studies of actual field sites show that plumes migrate more slowly than expected, reach a steady state, and decrease in extent and concentration when natural attenuation is occurring. Background dissolved oxygen levels greater than 1 to 2 mg/L and an inverse correlation between dissolved oxygen and contaminant levels have been identified through laboratory and field studies as key indicators of aerobic biodegradation. an important attenuation mechanism. Secondary indicators such as geochemical data, and more intensive methods such as contaminant mass balances, laboratory microcosm studies, and detailed ground water modeling can demonstrate natural attenuation as well. The recommended approach for evaluating natural attenuation is to design site assessment activities so that required data such as dissolved oxygen levels and historical plume flow path concentrations are obtained. With the necessary data, the primary indicators should be applied to evaluate natural attenuation. II the initial evaluation suggests that natural attenuation is a viable corrective action alternative, then a monitoring plan should be implemented to verify the extent of natural attenuation.     

Natural attenuation of volatile organic compounds (VOCs) in the leachate plume of a municipal landfill: using alkylbenzenes as process probes

More than 70 individual VOCs were identified in the leachate plume of a closed municipal landfill. Concentrations were low when compared with data published for other landfills, and total VOCs accounted for less than 0.1% of the total dissolved organic carbon. The VOC concentrations in the core of the anoxic leachate plume are variable, but in all cases they were found to be near or below detection limits within 200 m of the landfill. In contrast to the VOCs, the distributions of chloride ion, a conservative tracer, and nonvolatile dissolved organic carbon, indicate little dilution over the same distance. Thus, natural attenuation processes are effectively limiting migration of the VOC plume. The distribution of C2-3-benzenes, paired on the basis of their octanol-water partition coefficients and Henry's law constants, were systematically evaluated to assess the relative importance of volatilization, sorption, and biodegradation as attenuation mechanisms. Based on our data, biodegradation appears to be the process primarily responsible for the observed attenuation of VOCs at this site. We believe that the alkylbenzenes are powerful process probes that can and should be exploited in studies of natural attenuation in contaminated ground water systems.     

土壤水环境中有机污染物生物处理过程模型研究

生物处理是一种经济有效处理土壤水环境中有机污染物的手段,本文在研究土地生物处理过程的基础上,建立了综合描述有机污染物在土壤－水－微生物系统中扩散、吸附／解吸、屏蔽和生物降解过程的数学模型。为确定模型中各参数在模型计算中的作用和相对重要性,进行了参数灵敏度分析,预计数学模型可以定量预测有机污染物进行土地生物处理所需的要时间和程度,为构建土地生物处理工程提供参考。     

Migration of Chlorophenolic Compounds at the Chemical Waste Disposal Site at Alkali Lake, Oregon —1. Site Description and Ground-Water Flow

The hydrogeology of the chemical waste disposal site in the closed basin at Alkali Lake, Oregon has been examined. Interest in the site is due to the burial (November 1976) of 25,000 drums of herbicide manufacturing residues in unlined trenches on the playa of the basin. Included in the wastes were large amounts of chlorophenols and polymeric chlorophenoxyphenols. The flow of the alkaline (pH ∼10) ground water in the site area is driven by: (1) springs which create a mound east of the site; and (2) the sump effect of “West Alkali Lake,” a topographic low to the west of the site. Porosity, bulk mass densities, and grain-size distributions were determined. At one piezometer, the depth to ground water ranged between 0.9 m and 2.2 m. With the bottoms of the trenches in which the chemicals were buried between 0.60 and 0.75 m below the level of the ground surface, the bottom portions of the trenches may, at least occasionally, be in direct contact with the ground water.     

A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Natural Attenuation of Aromatic Hydrocarbons in a Shallow Sand Aquifer

Inadvertent release of petroleum products such as gasoline into the subsurface can initiate ground water contamination, particularly by the toxic, water-soluble and mobile gasoline components: benzene, toluene and xylenes (BTX). This study was undertaken to examine the processes controlling the rate of movement and the persistence of dissolved BTX in ground water in a shallow, unconfined sand aquifer.
Water containing about 7.6 mg/ L total BTX was introduced below the water table and the migration of contaminants through a sandy aquifer was monitored using a dense sampling network. BTX components migrated slightly slower than the ground water due to sorptive retardation. Essentially all the injected mass of BTX was lost within 434 days due to biodegradation. Rates of mass loss were similar for all monoaromatics; benzene was the only component to persist beyond 270 days. Laboratory biodegradation experiments produced similar rates, even when the initial BTX concentration varied.
A dominant control over BTX biodegradation was the availability of dissolved oxygen. BTX persisted at the field site in layers low in dissolved oxygen. Decreasing mass loss rates over time observed in the field experiment are not likely due to first-order deeradation rates, but rather to the persistence of small fractions of BTX mass in anoxic layers.     

Suitability of Polyvinyl Chloride Well Casings for Monitoring Munitions in Ground Water

A number of samples of polyvinyl chloride (PVC) well casings used for ground water monitoring that varied in schedule, diameter or manufacturer were placed in contact with low concentrations of aqueous solutions of TNT, RDX, HMX and 2,4-DNT for 80 days. Analysis indicated that there was more loss of TNT and HMX with the PVC casing than with the glass controls, but that the amount lost was, for the most part, equivalent among different types. A second experiment was performed to determine if these losses were due to sorption or if biodegradation was involved. Several different ground water conditions were simulated by varying salinity, initial pH and dissolved oxygen content. The only case where there was an in-creased loss of any substance due to the presence of PVC casing was with the TNT solution under non-sterile conditions. The extent of loss was small, however, considering the length of the equilibration period. This increased loss is thought to be associated with increased microbial degradation rather than sorption. Several samples of PVC casing were also leached with ground water for 80 days. No detectable interferences were found by reversed-phase high performance liquid chromatography (HPLC) analysis. Therefore, it is concluded that PVC well casings are suitable for monitoring ground water for the presence of these munitions.     

Enhanced Degradation of Dissolved Benzene and Toluene Using a Solid Oxygen-Releasing Compound

A field lest to evaluate the applicability of an oxygon-releasing compound (ORC) to the rernediation of ground water contaminated with benzone and toluene was conducted in the Borden Aquifer in Ontario. Canada. Benzene and toluene were injected as organic substrates to represent BTEX compounds, bromide was used as a tracer, and nitrate was added to avoid nitrate-limited conditions.
The fate of the solutes was monitored along four lines of monitoring points and wells. Two lines studied the behavior of the solutes upgradient and downgradient of two large-diameter well screens filled with briquets containing ORC and briquets without ORC. One line was used to study the solute behavior upgradient and downgradient of columns of ORC powder placed directly in the saturated zone. The remaining line was a control.
The results indicate that ORC in both briquet and powder form can release significant amounts of oxygen to conlaminated ground water passing by it. In the formulation used in this work, oxygen release persisted for at least 10 weeks. Furthemiore, the study indicates that the enhancement of the available dissolved oxygen content of at least 4 mg/L each of the ground water by ORC can support biodegradation of benzene and toluene dissolved in ground water. Such concentrations are typical of those encountered at sites contaminated with petroleum hydrocarbons; therefore, these results suggest that there is promise for ORC to enhance in situ biodegradation of BTKX contaminants at such sites using passive (nonpumping) systems to contact the contaminated ground water with the oxygen source.     

Modeling Management Practice Effects on Pesticide Movement to Ground Water

The assessment of agricultural impacts on water quality are now being redirected to include both ground water and surface water. Mathematical models have enhanced the ability of scientists'to evaluate these impacts. A variety of public domain models are available that can aid in evaluating the effects of managerial activities on pesticide movement to ground water. However, the ideal non-point source (NPS) pollution management model does not exist. Current models fail to adequately describe the transport of chemicals to ground water and, simultaneously, the effect of managerial practices on transport mechanisms. Much more work is necessary to develop a model that can describe water quality impacts of agricultural practices in a holistic framework that includes ground water and surface water concerns.     

Multidimensional analytical models for isotope ratios in groundwater pollutant plumes of organic contaminants undergoing different biodegradation kinetics

This work presents analytical models which are able to predict contours of concentrations and isotope ratios of organic pollutants in homogeneous aquifers. Four analytical solutions of the advective–dispersive transport equation for reactive transport from the literature differing in assumptions regarding biodegradation kinetics were used. Stable isotope ratios are computed after modelling the individual reactive transport of isotopic species in the aquifer, which respond differently to fractionation by biodegradation or sorption. The main finding of this study is that the isotope ratios in the plumes are very sensitive to the assumptions underlying the biodegradation kinetics in the models. When biodegradation occurs throughout the core of the plume as first-order reaction, the transversal gradients in isotope ratios are smooth. When biodegradation occurs in a bi-molecular reaction with an electron acceptor (modelled by double-Monod kinetics), steep transversal isotope gradients are predicted. When the reaction rates approach instantaneous reaction along the plume fringes, isotope shifts in the core of the plume disappear. A model incorporating plume and fringe degradation produces the most plausible predictions of isotope ratios in this study. It is shown furthermore that isotope fractionation by sorption causes an even different pattern of isotope ratios, with positive shifts restricted to near the forerunning front of an expanding plume. The models developed in this work can serve for the validation of numerical models and may be incorporated in natural attenuation support systems such as e.g. BIOSCREEN.     

BIOB: A mathematical model for the biodegradation of low solubility hydrocarbons

Modeling oil biodegradation is an important step in predicting the long term fate of oil on beaches. Unfortunately, existing models do not account mechanistically for environmental factors, such as pore water nutrient concentration, affecting oil biodegradation, rather in an empirical way. We present herein a numerical model, BIOB, to simulate the biodegradation of insoluble attached hydrocarbon. The model was used to simulate an experimental oil spill on a sand beach. The biodegradation kinetic parameters were estimated by fitting the model to the experimental data of alkanes and aromatics. It was found that parameter values are comparable to their counterparts for the biodegradation of dissolved organic matter. The biodegradation of aromatics was highly affected by the decay of aromatic biomass, probably due to its low growth rate. Numerical simulations revealed that the biodegradation rate increases by 3–4 folds when the nutrient concentration is increased from 0.2 to 2.0 mg N/L.     

Synergistic Application of Four Remedial Techniques at an Industrial Site

The soil and ground water at a General Motors plant site were contaminated with petroleum products from leaking underground storage tanks. Based on the initial assessment, the site was complex from the standpoint of geology (clay layers), hydrology (a recharge zone with a perched water table), and contaminant (approximately 4800 gallons of mixed gasoline and oil). After a thorough study of remedial alternatives, a synergistic remedial approach was adopted including pump and treat, product removal, vapor extraction, and bioventing. The system was designed and implemented at the site through 22 dual-extraction wells. Over a 21-month period, 4400 gallons of gasoline and oil were removed from the system, including 59 percent by vapor extraction, 28 percent by bioventing, and 13 percent by pump and treat. Synergism between the various remedial methods was demonstrated clearly. Ground water pump and treat lowered the water table, allowing air to flow for vapor extraction. The vacuum applied for vapor extraction increased the ground water removal rate and the efficiency of pump and treat. The vapor extraction system also added oxygen to the soil to stimulate aerobic biodegradation.     

Evaluation of volatilization as a natural attenuation pathway for MTBE

Volatilization and diffusion through the unsaturated zone can be an important pathway for natural attenuation remediation of methyl tert-butyl ether (MTBE) at gasoline spill sites. The significance of this pathway depends primarily on the distribution of immiscible product within the unsaturated zone and the relative magnitude of aqueous-phase advection (ground water recharge) to gaseous-phase diffusion. At a gasoline spill site in Laurel Bay, South Carolina, rates of MTBE volatilization from ground water downgradient from the source are estimated by analyzing the distribution of MTBE in the unsaturated zone above a solute plume. Volatilization rates of MTBE from ground water determined by transport modeling ranged from 0.0020 to 0.0042 g m(-2)/year, depending on the assumed rate of ground water recharge. Although diffusive conditions at the Laurel Bay site are favorable for volatilization, mass loss of MTBE is insignificant over the length (230 m) of the solute plume. Based on this analysis, significant volatilization of MTBE from ground water downgradient from source areas at other sites is not likely. In contrast, model results indicate that volatilization coupled with diffusion to the atmosphere could be a significant mass loss pathway for MTBE in source areas where residual product resides above the capillary zone. Although not documented, mass loss of MTBE at the Laurel Bay site due to volatilization and diffusion to the atmosphere are predicted to be two to three times greater than mass loading of MTBE to ground water due to dissolution and recharge. This result would imply that volatilization in the source zone may be the critical natural attenuation pathway for MTBE at gasoline spill sites, especially when considering capillary zone limitations on volatilization of MTBE from ground water and the relative recalcitrance of MTBE to biodegradation.     

Kinetic partitioning of Co,Mn, Cs,Fe, Ag,Zn and Cd in fresh waters (Loire) mixed with brackish waters (Loire estuary): experimental and modelling approaches

To simulate the behavior of radionuclides along a salinity gradient, in vitro sorption and desorption kinetics of Co, Mn, Cs, Fe, Ag, Zn and Cd were studied in Loire river water and the macrotidal Loire estuarine water over two different seasons. Partitioning between the dissolved phase and suspended solids were followed up over 100 h after adding radioactive tracers to freshly collected freshwater (sorption stage); this stage was followed by desorption in fresh and estuarine waters. A kinetic model describing the interactions between trace metals and particles under a salinity gradient was developed and calibrated. Among parameters and/or processes that control the fate and behavior of contaminated particles during their transfer in estuarine systems, this study shows that the speciation of trace metals is controlled by: (i) the chemical water composition: for all the elements except for Fe, desorption increased with salinity; however, the amplitude of such an effect strongly depended on the element and/or on the composition of the particulate phase (and consequently on the season); (ii) the possibility for a given element to form (or not) stable surface particle moieties such as oxides or inner-sphere complexes; (iii) the distribution of a given element among different types of sites characterised by different binding forces that can lead (or not) to re-adsorption processes after mixing of contaminated particles with uncontaminated water.Our model enabled the quantification of the contribution and the characteristic time of reactions that took place over short and long periods on the global partitioning between particulate and dissolved phases during sorption and desorption and to determine the extent to which these reactions were modified by the salinity.