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.     

Progression of natural attenuation processes at a crude-oil spill site: I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.     

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

High resolution direct-push profiling over short vertical distances was used to investigate CH(4) attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH(4) and CO(2), and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ(13)C(CH4) from an average of -57.6‰ (±1.7‰) in the methanogenic zone to -39.6‰ (±8.7‰) at 105m downgradient, strongly suggest CH(4) attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5m below the water table suggesting that transport of O(2) across the water table is leading to aerobic degradation of CH(4) at this interface. Dissolved N(2) concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O(2) through aerobic degradation of CH(4) or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O(2) rich recharge water were important O(2) transport mechanisms.     

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.     

A sequential zero valent iron and aerobic biodegradation treatment system for nitrobenzene

The remediation of nitroaromatic contaminated groundwater is sometimes difficult because nitroaromatic compounds are resistant to biodegradation and, when they do transform, the degradation of the products may also be incomplete. A simple nitroaromatic compound, nitrobenzene, was chosen to assess the feasibility of an in situ multi-zone treatment system at the laboratory scale. The proposed treatment system consists of a zero valent granular iron zone to reduce nitrobenzene to aniline, followed by a passive oxygen release zone for the aerobic biodegradation of the aniline daughter product using pristine aquifer material from Canadian Forces Base (CFB) Borden, Ontario, as an initial microbial source. In laboratory batch experiments, nitrobenzene was found to reduce quickly in the presence of granular iron forming aniline, which was not further degraded but remained partially sorbed onto the granular iron surface. Aniline was found to be readily biodegraded with little metabolic lag under aerobic conditions using the pristine aquifer material. A sequential column experiment, containing a granular iron reducing zone and an aerobic biodegradation zone, successively degraded nitrobenzene and then aniline to below detection limits (0.5 microM) without any noticeable reduction in hydraulic conductivity from biofouling, or through the formation of precipitates.     

Hexadecane and pristane degradation potential at the level of the aquifer—evidence from sediment incubations compared to in situ microcosms

Monitored natural attenuation is widely accepted as a sustainable remediation method. However, methods providing proof of proceeding natural attenuation within the water-unsaturated (vadose) zone are still relying on proxies such as measurements of reactive and non-reactive gases, or sediment sampling and subsequent mineralisation assays, under artificial conditions in the laboratory. In particular, at field sites contaminated with hydrophobic compounds, e.g. crude oil spills, an in situ evaluation of natural attenuation is needed, because in situ methods are assumed to provide less bias than investigations applying either proxies for biodegradation or off-site microcosm experiments. In order to compare the current toolbox of methods with the recently developed in situ microcosms, incubations with direct push-sampled sediments from the vadose and the aquifer zones of a site contaminated with crude oil were carried out in conventional microcosms and in situ microcosms. The results demonstrate the applicability of the in situ microcosm approach also outside water-saturated aquifer conditions in the vadose zone. The sediment incubation experiments demonstrated turnover rates in a similar range (vadose, 4.7 mg/kg*day; aquifer, 6.4 mg_hexadecane/kg_soil/day) of hexadecane degradation in the vadose zone and the aquifer, although mediated by slightly different microbial communities according to the analysis of fatty acid patterns and amounts. Additional experiments had the task of evaluating the degradation potential for the branched-chain alkane pristane (2,6,10,14-tetramethylpentadecane). Although this compound is regarded to be hardly degradable in comparison to n-alkanes and is thus frequently used as a reference parameter for indexing the extent of biodegradation of crude oils, it could be shown to be degraded by means of the incubation experiments. Thus, the site had a high inherent potential for natural attenuation of crude oils both in the vadose zone and the aquifer.     

Transport of Escherichia coli and solutes during waste water infiltration in an urban alluvial aquifer

Recharge of waste water in an unconsolidated poorly sorted alluvial aquifer is a complex process, both physically and hydrochemically. The aim of this paper is to analyse and conceptualise vertical transport mechanisms taking place in an urban area of extensive wastewater infiltration by analysing and combining the water balance, the microbial (Escherichia coli) mass balance, and the mass balance for dissolved solutes. For this, data on sediment characteristics (grain size, organic carbon, reactive iron, and calcite), groundwater levels, and concentrations of E. coli in groundwater and waste water were collected. In the laboratory, data on E. coli decay rate coefficients, and on bacteria retention characteristics of the sediment were collected via column experiments. The results indicated that shallow groundwater, at depths of 50 m below the surface, was contaminated with E. coli concentrations as high as 10(6) CFU/100 mL. In general, E. coli concentrations decreased only 3 log units from the point of infiltration to shallow groundwater. Concentrations were lower at greater depths in the aquifer. In laboratory columns of disturbed sediments, bacteria removal was 2-5 log units/0.5 cm column sediment. Because of the relatively high E. coli concentrations in the shallow aquifer, transport had likely taken place via a connected network of pores with a diameter large enough to allow bacterial transport instead of via the sediment matrix, which was inaccessible for bacteria, as was clear from the column experiments. The decay rate coefficient was determined from laboratory microcosms to be 0.15 d(-1). Assuming that decay in the aquifer was similar to decay in the laboratory, then the pore water flow velocity between the point of infiltration and shallow groundwater, coinciding with a concentration decrease of 3 log units, was 0.38 m/d, and therefore, transport in this connected network of pores was fast. According to the water balance of the alluvial aquifer, determined from transient groundwater modelling, groundwater flow in the aquifer was mainly in vertical downward direction, and therefore, the mass balance for dissolved solutes was simulated using a 1D transport model of a 200 m column of the Quaternary Alluvium aquifer. The model, constructed with PHREEQC, included dual porosity, and was able to adequately simulate removal of E. coli, cation-exchange, and nitrification. The added value of the use of E. coli in this study was the recognition of relatively fast transport velocities occurring in the aquifer, and the necessity to use the dual porosity concept to investigate vertical transport mechanisms. Therefore, in general and if possible, microbial mass balances should be considered more systematically as an integral part of transport studies.     

Sequential anaerobic-aerobic treatment of an aquifer contaminated by halogenated organics: field results

In situ, sequential, anaerobic to aerobic treatment of groundwater removed perchloroethene (PCE, 1.1 microM) and benzene (0.8 microM) from a contaminated aquifer. Neither aerobic nor anaerobic treatment alone successfully degraded both the chlorinated and non-chlorinated organic contaminants in the aquifer. After the sequential treatment, PCE, trichloroethene (TCE), vinyl chloride (VC), chloroethane (CA), and benzene were not detectable in groundwater. Desorption of residual aquifer contaminants was tested by halting the groundwater recirculation and analyzing the groundwater after 3 and 7 weeks. No desorption of the chlorinated contaminants or daughter products was observed in the treated portion of the aquifer. Sequential anaerobic to aerobic treatment was successful in remediating the groundwater at this test site and may have broad applications at other contaminated sites. Over the 4-year course of the project, the predominant microbial environment of the test site varied from aerobic to sulfate-reducing, to methanogenic, and back to aerobic conditions. Metabolically active microbial populations developed under all conditions, demonstrating the diversity and robustness of natural microbial flora in the aquifer.     

An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 mumol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH4 and CO2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.     

Mineralization of PAHs in coal-tar impacted aquifer sediments and associated microbial community structure investigated with FISH

The microbial community structure and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a coal-tar contaminated aquifer were investigated spatially using fluorescence in situ hybridization (FISH) and in laboratory-scale incubations of the aquifer sediments. DAPI-detected microbial populations in the contaminated sediments were three orders of magnitude greater than nearby uncontaminated sediments, suggesting growth on coal-tar constituents in situ. Actinobacteria, beta- and gamma-Proteobacteria, and Flavobacteria dominated the in situ aerobic (>1 mg l(-1) dissolved oxygen) microbial community, whereas sulfate-reducing bacteria comprised 37% of the microbial community in the sulfidogenic region of the aquifer. Rapid mineralization of naphthalene and phenanthrene were observed in aerobic laboratory microcosms and resulted in significant enrichment of beta- and gamma-Proteobacteria potentially explaining their elevated presence in situ. Firmicutes, Flavobacteria, alpha-Proteobacteria, and Actinobacteria were also enriched in the mineralization assays, but to a lesser degree. Nitrate- and sulfate-limited mineralization of naphthalene in laboratory microcosms occurred to a small degree in aquifer sediments from locations where groundwater chemistry indicated nitrate- and sulfate-reduction, respectively. Some iron-limited mineralization of naphthalene and phenanthrene was also observed in sediments originating near groundwater measurements of elevated ferrous iron. The results of this study suggest that FISH may be a useful tool for providing a much needed link between laboratory microcosms and groundwater measurements made in situ necessary to better demonstrate the potential for natural attenuation at complex PAH contaminated sites.     

Impact of edible oil injection on the permeability of aquifer sands

Recent laboratory and field studies have shown that food-grade edible oils can be injected into the subsurface for installation of in-situ permeable reactive barriers. However to be effective, the oil must be distributed out away from the oil injection points without excessive permeability loss. In this work, we examine the distribution of soybean oil in representative aquifer sediments as non-aqueous phase liquid oil (NAPL oil) or as an oil-in-water emulsion. Laboratory columns packed with sands or clayey sands were flushed with either NAPL oil or a soybean emulsion followed by plain water, while monitoring permeability loss and the final oil residual saturation. NAPL oil can be injected into coarse-grained sands. However NAPL injection into finer grained sediments requires high injection pressures which may not be feasible at some sites. In addition, NAPL injection results in high oil residual saturations and moderate permeability losses. In contrast, properly prepared emulsions can be distributed through sands with varying clay content without excessive pressure buildup, low oil retention and very low to moderate permeability loss. For effective transport, the emulsion must be stable, the oil droplets must be significantly smaller than the mean pore size of the sediment and the oil droplets should have a low to moderate tendency to stick to each other and the aquifer sediments. In our work, oil retention and associated permeability loss increased with sediment clay content and with the ratio of droplet size to pore size. For sandy sediments, the permeability loss is modest (0-40% loss) and is proportional to the oil residual saturation.     

Air distribution in the Borden aquifer during in situ air sparging

A field experiment was conducted at Canadian Forces Base Borden (CFB Borden) to assess the air distribution from a single in situ air sparging injection point. This aquifer consists of fine to medium sand deposited in horizontal layers. The permeability at the study location varied from 10(-10) to 10(-14) m2 and distinct low permeability horizons were present at approximately 1.2, 2.0, and 2.9 m below the water table. Prior to air injection, a 15x15-m portion of the vadose zone was excavated to the water table (approximately 1 m below ground surface) in order to visually observe air release distribution at the water table. The water table was actively maintained 5 cm above the excavated surface. The sparging system operated for a period of 7 days with an injection flow rate of 200 m3/days (5 scfm). The resulting subsurface air distribution was assessed using a variety of techniques including neutron logging, borehole and surface ground penetrating radar, piezometric head measurements, surface visualization, and hydraulic testing. Through this combination of tests, it was demonstrated that variations in permeability and, hence, capillary pressure at the site were sufficient to cause the injected air to spread laterally, forming stratigraphically trapped air pockets beneath the low permeability horizons. The formation of these air pockets eventually resulted in a buildup of capillary pressure that exceeded the air entry pressure and allowed some air to migrate up through the lower permeability layers. Each of the assessment techniques employed generated information at different spatial scales that prevented a direct comparison of the results from the various techniques; however, the results from all techniques proved to be critical in the interpretation of the experimental data. As a consequence, the different assessment techniques should not be viewed as alternatives, but rather as complimentary techniques.     

Laboratory studies to characterize the efficacy of sand capping a coal tar-contaminated sediment

Placement of a microbial active sand cap on a coal tar-contaminated river sediment has been suggested as a cost effective remediation strategy. This approach assumes that the flux of contaminants from the sediment is sufficiently balanced by oxygen and nutrient fluxes into the sand layer such that microbial activity will reduce contaminant concentrations within the new benthic zone and reduce the contaminant flux to the water column. The dynamics of such a system were evaluated using batch and column studies with microbial communities from tar-contaminated sediment under different aeration and nutrient inputs. In a 30-d batch degradation study on aqueous extracts of coal tar sediment, oxygen and nutrient concentrations were found to be key parameters controlling the degradation rates of polycyclic aromatic hydrocarbons (PAHs). For the five PAHs monitored (naphthalene, fluorene, phenanthrene, anthracene, and pyrene), degradation rates were inversely proportional to molecular size. For the column studies, where three columns were packed with a 20-cm sand layer on the top of a 5 cm of sediment layer, flow was established to sand layers with (1) aerated water, (2) N(2) sparged water, or (3) HgCl(2)-sterilized N(2) sparged water. After steady-state conditions, PAH concentrations in effluents were the lowest in the aerated column, except for pyrene, whose concentration was invariant with all effluents. These laboratory scale studies support that if sufficient aeration can be achieved in the field through either active and passive means, the resulting microbially active sand layer can improve the water quality of the benthic zone and reduce the flux of many, but not all, PAHs to the water column.     

Anaerobic biodegradation of alkylbenzenes and trichloroethylene in aquifer sediment down gradient of a sanitary landfill

The objective of this investigation was to evaluate the anaerobic biodegradability of benzene, toluene, ethylbenzene, ortho-, meta- and para-xylene (BTEX) and trichloroethylene (TCE) in aquifer sediment down gradient of an unlined landfill. The major organic contaminants identified in the shallow unconfined aquifer are cis-dichloroethylene (c-DCE) and toluene. The biodegradative potential of the contaminated aquifer was measured in three sets of microcosms constructed using anaerobic aquifer sediment from three boreholes down gradient of the landfill. The degradability of BTEX and TCE was examined under ambient and amended conditions. TCE was degraded in microcosms with aquifer material from all three boreholes. Toluene biodegradation was inconsistent, exhibiting biodegradation with no lag in one set of microcosms but more limited biodegradation in two additional sets of microcosms. TCE exhibited an inhibitory effect on toluene degradation at one location. The addition of calcium carbonate stimulated TCE biodegradation which was not further stimulated by nutrient addition. TCE was converted to ethylene, a harmless byproduct, in all tests. Benzene, ethylbenzene and xylene isomers were recalcitrant in both ambient and amendment experiments. Biodegradation occurred under methanogenic conditions as methane was produced in all experiments. Bromoethane sulfonic acid (BES), a methanogenic inhibitor, inhibited methane and ethylene production and TCE biodegradation. The results indicate the potential for intrinsic bioremediation of TCE and toluene down gradient of the Wilder's Grove, North Carolina, landfill. The low concentrations of TCE in monitoring wells was consistent with its biodegradation in laboratory microcosms.     

Modeling steady-state methanogenic degradation of phenols in groundwater

Field and microcosm observations of methanogenic phenolic compound degradation indicate that Monod kinetics governs the substrate disappearance but overestimates the observed biomass. In this paper we present modeling results from an ongoing multidisciplinary study of methanogenic biodegradation of phenolic compounds in a sand and gravel aquifer contaminated by chemicals and wastes used in wood treatment. Field disappearance rates of four phenols match those determined in batch microcosm studies previously performed by E.M. Godsy and coworkers. The degradation process appears to be at steady-state because even after a sustained influx over several decades, the contaminants still are disappearing in transport downgradient. The existence of a steady-state degradation profile of each substrate together with a low biomass density in the aquifer indicate that the bacteria population is exhibiting no net growth. This may be due to the oligotrophic nature of the biomass population in which utilization and growth are approximately independent of concentration for most of the concentration range. Thus a constant growth rate should exist over much of the contaminated area which may in turn be balanced by an unusually high decay or maintenance rate due to hostile conditions or predation.     

Effects of source zone heterogeneity on surfactant-enhanced NAPL dissolution and resulting remediation end-points

The effectiveness of removal of nonaqueous phase liquids (NAPLs) from the entrapment source zone of the subsurface has been limited by soil heterogeneity and the inability to locate all entrapped sources. The goal of this study was to demonstrate the uncertainty of degree of source removal associated with aquifer heterogeneity. In this demonstration, source zone NAPL removal using surfactant-enhanced dissolution was considered. Model components that simulate the processes of natural dissolution in aqueous phase and surfactant-enhanced dissolution were incorporated into an existing code of contaminant transport. The dissolution modules of the simulator used previously developed Gilland-Sherwood type phenomenological models of NAPL dissolution to estimate mass transfer coefficients that are upscaleable to multidimensional flow conditions found at field sites. The model was used to simulate the mass removal from 10 NAPL entrapment zone configurations based on previously conducted two-dimensional tank experiments. These entrapment zones represent the NAPL distribution in spatially correlated random fields of aquifer hydraulic conductivity. The numerical simulations representing two-dimensional conditions show that effectiveness of mass removal depends on the aquifer heterogeneity that controls the NAPL entrapment and delivery of the surfactant to the locations of entrapped NAPLs. Flow bypassing resulting from heterogeneity and the reduction of relative permeability due to NAPL entrapment reduces the delivery efficiency of the surfactant, thus prolonging the remediation time to achieve desired end-point NAPL saturations and downstream dissolved concentrations. In some extreme cases, the injected surfactant completely bypassed the NAPL source zones. It was also found that mass depletion rates for different NAPL source configurations vary significantly. The study shows that heterogeneity result in uncertainties in the mass removal and achievable end-points that are directly related to dissolved contaminant plume development downstream of the NAPL entrapment zone.     

The significance of heterogeneity on mass flux from DNAPL source zones: an experimental investigation

Understanding the process of mass transfer from source zones of aquifers contaminated with organic chemicals in the form of dense non-aqueous phase liquids (DNAPL) is of importance in site management and remediation. A series of intermediate-scale tank experiments was conducted to examine the influence of aquifer heterogeneity on DNAPL mass transfer contributing to dissolved mass emission from source zone into groundwater under natural flow before and after remediation. A Tetrachloroethylene (PCE) spill was performed into six source zone models of increasing heterogeneity, and both the spatial distribution of the dissolution behavior and the net effluent mass flux were examined. Experimentally created initial PCE entrapment architecture resulting from the PCE migration was largely influenced by the coarser sand lenses and the PCE occupied between 30 and 60% of the model aquifer depth. The presence of DNAPL had no apparent effect on the bulk hydraulic conductivity of the porous media. Up to 71% of PCE mass in each of the tested source zone was removed during a series of surfactant flushes, with associated induced PCE mobilization responsible for increasing vertical DNAPL distributions. Effluent mass flux due to water dissolution was also found to increase progressively due to the increase in NAPL-water contact area even though the PCE mass was reduced. Doubling of local groundwater flow velocities showed negligible rate-limited effects at the scale of these experiments. Thus, mass transfer behavior was directly controlled by the morphology of DNAPL within each source zone. Effluent mass flux values were normalized by the up-gradient DNAPL distributions. For the suite of aquifer heterogeneities and all remedial stages, normalized flux values fell within a narrow band with mean of 0.39 and showed insensitivity to average source zone saturations.     

Degradation of herbicides in two sandy aquifers under different redox conditions.

We examined the potential for complete degradation (mineralisation) of the four [ring-U-14C]herbicides mecoprop, isoproturon, atrazine, and metsulphuron-methyl in two sandy aquifers representing aerobic, denitrifying, sulphate-reducing, and methanogenic conditions. Slurries with sediment and groundwater were set-up aerobically or anaerobically in the presence of the electron-acceptor prevailing at the sampling site, amended with 25 microg l(-1) herbicide, and incubated at 10 degrees C. Considerable mineralisation was only observed in sediment from the plough layer incubated aerobically. Here, 30% of 14C-mecoprop was recovered as 14CO2 after 15 days and 15% of isoproturon was recovered as 14CO2 after 267 days. Only 7% of mecoprop was recovered as 14CO2 after 313 days in sediment from the aquifer below sampled at 1.95-3.00 mbs (m below the surface). In denitrifying and methanogenic slurries, 3% of 14C added as mecoprop was recovered as 14CO2. Isoproturon was not mineralised except in the aerobic plough layer, and atrazine and metsulphuron-methyl were not mineralised under any of the conditions applied.     

Inherent mineralization of 2,6-dichlorobenzamide (BAM) in unsaturated zone and aquifers--effect of initial concentrations and adaptation

The dichlobenil metabolite BAM (2,6-dichlorobenzamide) is frequently detected in aquifers e.g. in Denmark despite the mother compound dichlobenil was banned here since 1997. BAM mineralization was investigated at environmentally relevant concentrations in sediment samples. Undisturbed sediment cores with known dichlobenil application were collected from topsoil to 8.5 m below surface resulting in 57 samples hereof 4 aquifer samples. Mineralization was only substantial (>10%) in the uppermost meter of the unsaturated zone. Microbial adaptation, observed as faster mineralization in pre-exposed than in pristine sediments from the same location, was only evident in sandy sediment where dichlobenil was still present, but not in clayey sediments. Higher initial concentrations (1-5000 μg/kg) did not stimulate mineralization in pristine clayey or sandy sediments, or in pre-exposed sand. However, in pre-exposed clay mineralization was stimulated at high concentrations. Furthermore BAM was for the first time mineralized in aerobic aquifer sediments from different BAM-contaminated groundwater locations.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.