Heavy contamination of a subsurface aquifer and a stream by livestock wastewater in a stock farming area, Wonju, Korea

A survey of groundwater and stream water quality was undertaken in a stock farming area where livestock wastewater infiltrates into sandy unsaturated zones and saturated bedrock aquifers containing fractures. To determine the degree of contamination and track the effect of livestock wastewater on groundwater and stream water quality, the population of indicator bacteria (total coliforms, fecal coliforms, fecal streptococci, Staphylococcus spp., and sulfite-reducing clostridia) together with relevant physicochemical parameters were monitored along the wastewater flow-pathways over a 19-month period. The stream water was severely contaminated with livestock wastewater. Nearly all physicochemical and bacteriological parameters in the stream water were much greater than those in the groundwater. Nitrate-N concentrations ranged from 10.0 to 20.0 mg l(-1) in boreholes located downstream (site C) from the livestock waste disposal site, while those in the background borehole (W2) were below 1.0 mg l(-1). Densities of indicator bacteria in boreholes at site C were two or three orders of magnitude higher than those in W2 borehole. In boreholes located downstream from the livestock waste disposal site, the concentration of ammonium-N, nitrate-N, and pollution indicator bacteria increased as groundwater level rose due to infiltration of rainwater. In W2 borehole, however, physicochemical parameters and the number of pollution indicator bacteria had no correlation with the groundwater level. Collectively, these results suggest that the deep aquifers were heavily contaminated with infiltrated livestock wastewater, which consequently must be adequately treated to minimize groundwater pollution.     

Coalbed methane produced water in China: status and environmental issues

As one of the unconventional natural gas family members, coalbed methane (CBM) receives great attention throughout the world. The major associated problem of CBM production is the management of produced water. In the USA, Canada, and Australia, much research has been done on the effects and management of coalbed methane produced water (CMPW). However, in China, the environmental effects of CMPW were overlooked. The quantity and the quality of CMPW both vary enormously between coal basins or stratigraphic units in China. The unit produced water volume of CBM wells in China ranges from 10 to 271,280 L/well/day, and the concentration of total dissolved solids (TDS) ranges from 691 to 93,898 mg/L. Most pH values of CMPW are more than 7.0, showing the alkaline feature, and the Na-HCO₃ and Na-HCO₃-Cl are typical types of CMPW in China. Treatment and utilization of CMPW in China lag far behind the USA and Australia, and CMPW is mainly managed by surface impoundments and evaporation. Currently, the core environmental issues associated with CMPW in China are that the potential environmental problems of CMPW have not been given enough attention, and relevant regulations as well as environmental impact assessment (EIA) guidelines for CMPW are still lacking. Other potential issues in China includes (1) water quality monitoring issues for CMPW with special components in special areas, (2) groundwater level decline issues associated with the dewatering process, and (3) potential environmental issues of groundwater pollution associated with hydraulic fracturing.     

Nitrogen as an indicator of mass transfer during in-situ gas sparging

Aiming at the stimulation of intrinsic microbial activity, pulses of pure oxygen or pressurized air were recurrently injected into groundwater polluted with chlorobenzene. To achieve well-controlled conditions and intensive sampling, a large, vertical underground tank was filled with the local unconfined sandy aquifer material. In the course of two individual gas injections, one using pure oxygen and one using pressurized air, the mass transfer of individual gas species between trapped gas phase and groundwater was studied. Field data on the dissolved gas composition in the groundwater were combined with a kinetic model on gas dissolution and transport in porous media. Phase mass transfer of individual gas components caused a temporary enrichment of nitrogen, and to a lower degree of methane, in trapped gas leading to the formation of excess dissolved nitrogen levels downgradient from the dissolving gas phase. By applying a novel gas sampling method for dissolved gases in groundwater it was shown that dissolved nitrogen can be used as a partitioning tracer to indicate complete gas dissolution in porous media.     

The flux of radionuclides in flowback fluid from shale gas exploitation

This study considers the flux of radioactivity in flowback fluid from shale gas development in three areas: the Carboniferous, Bowland Shale, UK; the Silurian Shale, Poland; and the Carboniferous Barnett Shale, USA. The radioactive flux from these basins was estimated, given estimates of the number of wells developed or to be developed, the flowback volume per well and the concentration of K (potassium) and Ra (radium) in the flowback water. For comparative purposes, the range of concentration was itself considered within four scenarios for the concentration range of radioactive measured in each shale gas basin, the groundwater of the each shale gas basin, global groundwater and local surface water. The study found that (i) for the Barnett Shale and the Silurian Shale, Poland, the 1 % exceedance flux in flowback water was between seven and eight times that would be expected from local groundwater. However, for the Bowland Shale, UK, the 1 % exceedance flux (the flux that would only be expected to be exceeded 1 % of the time, i.e. a reasonable worst case scenario) in flowback water was 500 times that expected from local groundwater. (ii) In no scenario was the 1 % exceedance exposure greater than 1 mSv—the allowable annual exposure allowed for in the UK. (iii) The radioactive flux of per energy produced was lower for shale gas than for conventional oil and gas production, nuclear power production and electricity generated through burning coal.     

Humic colloid-borne migration of uranium in sand columns

Column experiments were carried out to investigate the influence of humic colloids on subsurface uranium migration. The columns were packed with well-characterized aeolian quartz sand and equilibrated with groundwater rich in humic colloids (dissolved organic carbon (DOC): 30 mg dm(-3)). U migration was studied under an Ar/1% CO2 gas atmosphere as a function of the migration time, which was controlled by the flow velocity or the column length. In addition, the contact time of U with groundwater prior to introduction into a column was varied. U(VI) was found to be the dominant oxidation state in the spiked groundwater. The breakthrough curves indicate that U was transported as a humic colloid-borne species with a velocity up to 5% faster than the mean groundwater flow. The fraction of humic colloid-borne species increases with increasing prior contact time and also with decreasing migration time. The migration behavior was attributed to a kinetically controlled association/dissociation of U onto and from humic colloids and also a subsequent sorption of U onto the sediment surface. The column experiments provide an insight into humic colloid-mediated U migration in subsurface aquifers.     

Mercury sorption to sediments: dependence on grain size, dissolved organic carbon, and suspended bacteria

A combination of laboratory scale derived correlations and measurements of grain size distribution, DOC (dissolved organic carbon) concentration, and density of suspended bacteria promises to be useful in estimating Hg(II) sorption in heterogeneous streambeds and groundwater environments. This was found by shaking intact sediment and fractions thereof (<63-2000mum) with solutions of HgCl(2) (1.0-10.0ngml(-1)). The intact sediment was also shaken with the Hg(II) solutions separately in presence of DOC (6.5-90.2mugml(-1)) or brought in contact with suspensions of a strain of groundwater bacteria (2x10(4)-2x10(6)cellsml(-1)). Hg(II) sorption was rather weak and positively correlated with the grain size, and the sorption coefficient (K(d)) varied between about 300 and 600mlg(-1). By using the relative surface areas of the fractions, K(d) for the intact sediment was back calculated with 2% deviation. K(d) was negatively correlated with the concentration of DOC and positively correlated with the number of bacteria. A multiple regression showed that K(d) was significantly more influenced by the number of bacteria than by the grain size. The findings imply that common DOC concentrations in groundwater and streambeds, 5-20mugml(-1), will halve the K(d) obtained from standard sorption assays of Hg(II), and that K(d) will almost double when the cell numbers are doubled at densities that are common in aquifers. The findings suggest that simultaneous measurements of surface areas of sediment particles, DOC concentrations, and bacterial numbers are useful to predict spatial variation of Hg(II) sorption in aquifers and sandy sediments.     

Degradation of the herbicide dichlobenil and its metabolite BAM in soils and subsurface sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in surface water and groundwater. To evaluate the potential for natural attenuation of this BAM pollution in groundwater, we studied the degradation of BAM and dichlobenil in 16 samples of clayey till, unconsolidated sand and limestone, including sediments from both oxidized and reduced conditions. The degradation of dichlobenil occurred primarily in the upper few meters below surface, although dichlobenil was strongly sorbed to these sediments. However, the degradation of dichlobenil to BAM could not be correlated to either sorption, water chemistry, composition of soils or sediments. Degradation of dichlobenil to BAM was limited (<2% degraded) in the deeper unsaturated zones, and no degradation was observed in aquifer sediments. This illustrates, that dichlobenil transported to aquifers does not contribute to the BAM-contamination in aquifers. A small, but significant degradation of BAM was observed in the upper part of the unsaturated zones in sandy sediments, but no degradation was observed in the clayey till sediment or in the deeper unsaturated zones. The insignificant degradation of BAM in aquifer systems shows that BAM pollution detected in aquifers will appear for a long time; and consequently the potential for natural attenuation of BAM in aquifer systems is limited.     

Greenhouse gas emission potential of the municipal solid waste disposal sites in Thailand

Open dumping and landfilling are the prevalent solid waste disposal practices in Thailand. Surveys on the disposal sites revealed the presence of 95 landfills and 330 open dumps. Methane emission potential at these sites was estimated by three methods. Results of the Intergovernmental Panel on Climate Change (IPCC) method, Landfill Gas Emission model (LandGEM), and closed flux chamber technique were compared. The methane emission potential of 366 Gg/yr using the IPCC method was higher than the estimations of the LandGEM and closed flux chamber method of 115 Gg/yr and 103 Gg/yr, respectively. An understanding of the methane emission potential initiated the analysis of upgrading the open dumps into landfills, adding landfills to meet the future needs and utilization of landfill gases. Upgrading the open dumps to landfills increased the methane emission rates and their utilization potential. Approximately 20 additional landfills may be required to meet future demands. Landfill gas (LFG) utilization appears to be feasible in the large-scale landfills.     

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

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

Sediment filled fractures in the Permo-Triassic sandstones of the Cheshire basin: observations and implications for pollutant transport

Fracture mapping in a tunnel system and at nearby outcrop on the Runcorn Penninsula, UK, suggests the need for a review of the potential pathways for pollutant transport in Permo-Triassic sandstone aquifers. Sediment infilling is pervasive in the largest sub-vertical multi-layer fractures in the study area, both at the surface and to a depth of about 40 m below ground level. Sediment infill is inferred to have formed in situ. The conventional models of pollutant transport in fracture networks assume that they comprise open fractures, with pollutant mobility depending on fracture connectivity (a function of density, length, orientation and intersection) and aperture. The presence of extensive sediment fills in fractures will materially change their permeability, thereby reducing pollutant flux, and be of significance in the assessment of risks arising from chemical spillages. There has been little or no substantive evidence for such fills in Permo-Triassic sandstones in the UK, apart from observations at outcrop and anecdotes of sand being pumped from boreholes. Here, we report surface and rare, but complementary, subsurface observations of extensive fills in the Cheshire basin, and argue that they will only act as preferential pathways where they crosscut low-permeability horizons such as mudstones.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

Radon as a naturally occurring tracer for the assessment of residual NAPL contamination of aquifers

The noble gas radon has a strong affinity to non-aqueous phase-liquids (NAPLs). That property makes it applicable as naturally occurring partitioning tracer for assessing residual NAPL contamination of aquifers. In a NAPL contaminated aquifer, radon dissolved in the groundwater partitions preferably into the NAPL. The magnitude of the resulting radon deficit in the groundwater depends on the NAPL-specific radon partition coefficient and on the NAPL saturation of the pore space. Hence, if the partition coefficient is known, the NAPL saturation is attainable by determination of the radon deficit. After a concise discussion of theoretical aspects regarding radon partitioning into NAPL, related experimental data and results of a field investigation are presented. Aim of the laboratory experiments was the determination of radon partition coefficients of multi-component NAPLs of environmental concern. The on-site activities were carried out in order to confirm the applicability of the "radon method" under field conditions.     

Microbiological analysis of multi-level borehole samples from a contaminated groundwater system

A range of bacteriological, geochemical process-related and molecular techniques have been used to assess the microbial biodegradative potential in groundwater contaminated with phenol and other tar acids. The contaminant plume has travelled 500 m from the pollutant source over several decades. Samples were obtained from the plume using a multi-level sampler (MLS) positioned in two boreholes (boreholes 59 and 60) which vertically transected two areas of the plume. Activity of the microbial community, as represented by phenol degradation potential and ability to utilise a range of substrates, was found to be influenced by the plume. Phenol degradation potential appeared to be influenced more by the concentration of the contaminants than the total bacterial cell numbers. However, in the areas of highest phenol concentration, the depression of cell numbers clearly had an effect. The types of bacteria present were assessed by culture and DNA amplification by polymerase chain reaction (PCR). Bacterial groups or processes associated with major geochemical processes, such as methanogenesis, sulphate reduction and denitrification, that have the potential to drive contaminant degradation, were detected at various borehole levels. A comparative molecular analysis of the microbial community between samples obtained from the MLS revealed the microbial community was diverse. The examination of microbial activity complemented those results obtained through chemical analysis, and when combined with hydrological data, showed that MLS samples provided a realistic profile of plume effects and could be related to the potential for natural attenuation of the site.     

Comparing estimates of fugitive landfill methane emissions using inverse plume modeling obtained with Surface Emission Monitoring (SEM), Drone Emission Monitoring (DEM), and Downwind Plume Emission Monitoring (DWPEM)

ABSTRACT

As part of the global effort to quantify and manage anthropogenic greenhouse gas emissions, there is considerable interest in quantifying methane emissions in municipal solid waste landfills. A variety of analytical and experimental methods are currently in use for this task. In this paper, an optimization-based estimation method is employed to assess fugitive landfill methane emissions. The method combines inverse plume modeling with ambient air methane concentration measurements. Three different measurement approaches are tested and compared. The method is combined with surface emission monitoring (SEM), above ground drone emission monitoring (DEM), and downwind plume emission monitoring (DWPEM). The methodology is first trialed and validated using synthetic datasets in a hand-generated case study. A field study is also presented where SEM, DEM and DWPEM are tested and compared. Methane flux during two-days measurement campaign was estimated to be between 228 and 350 g/s depending on the type of measurements used. Compared to SEM, using unmanned aerial systems (UAS) allows for a rapid and comprehensive coverage of the site. However, as showed through this work, advancement of DEM-based methane sampling is governed by the advances that could be made in UAS-compatible measurement instrumentations. Downwind plume emission monitoring led to a smaller estimated flux compared with SEM and DEM without information about positions of major leak points in the landfill. Even though, the method is simple and rapid for landfill methane screening. Finally, the optimization-based methodology originally developed for SEM, shows promising results when it is combined with the drone-based collected data and downwind concentration measurements. The studied cases also discovered the limitations of the studied sampling strategies which is exploited to identify improvement strategies and recommendations for a more efficient assessment of fugitive landfill methane emissions.

Implications: Fugitive landfill methane emission estimation is tackled in the present study. An optimization-based method combined with inverse plume modeling is employed to treat data from surface emission monitoring, drone-based emission monitoring and downwind plume emission monitoring. The study helped revealing the advantages and the limitations of the studied sampling strategies. Recommendations for an efficient assessment of landfill methane emissions are formulated. The method trialed in this study for fugitive landfill methane emission could also be appropriate for rapid screening of analogous greenhouse gas emission hotspots.     

A direct passive method for measuring water and contaminant fluxes in porous media

This paper introduces a new direct method for measuring water and contaminant fluxes in porous media. The method uses a passive flux meter (PFM), which is essentially a self-contained permeable unit properly sized to fit tightly in a screened well or boring. The meter is designed to accommodate a mixed medium of hydrophobic and/or hydrophilic permeable sorbents, which retain dissolved organic/inorganic contaminants present in the groundwater flowing passively through the meter. The contaminant mass intercepted and retained on the sorbent is used to quantify cumulative contaminant mass flux. The sorptive matrix is also impregnated with known amounts of one or more water soluble 'resident tracers'. These tracers are displaced from the sorbent at rates proportional to the groundwater flux; hence, in the current meter design, the resident tracers are used to quantify cumulative groundwater flux. Theory is presented and quantitative tools are developed to interpret the water flux from tracers possessing linear and nonlinear elution profiles. The same theory is extended to derive functional relationships useful for quantifying cumulative contaminant mass flux. To validate theory and demonstrate the passive flux meter, results of multiple box-aquifer experiments are presented and discussed. From these experiments, it is seen that accurate water flux measurements are obtained when the tracer used in calculations resides in the meter at levels representing 20 to 70 percent of the initial condition. 2,4-Dimethyl-3-pentanol (DMP) is used as a surrogate groundwater contaminant in the box aquifer experiments. Cumulative DMP fluxes are measured within 5% of known fluxes. The accuracy of these estimates generally increases with the total volume of water intercepted.     

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

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

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.     

An analytical solution for vertical transport of volatile chemicals in the vadose zone

An analytical solution is presented for one-dimensional vertical transport of volatile chemicals through the vadose zone to groundwater. The solution accounts for the important transport mechanisms of the steady advection of water and gas, diffusion and dispersion in water and gas, as well as adsorption, and first-order degradation. By assuming a linear, equilibrium partitioning between water, gas and the adsorbed chemical phases, the dependent variable in the mathematical model becomes the total resident concentration. The general solution was derived for cases having a constant initial total concentration over a discrete depth interval and a zero initial total concentration elsewhere. A zero concentration gradient is assumed at the groundwater table. Examples are given to demonstrate the application of the new solution for calculating the case of a non-uniform initial source concentration, and estimating the transport of chemicals to the groundwater and the atmosphere. The solution was also used to verify a numerical code called VLEACH. We discovered an error in VLEACH, and found that the new solution agreed very well with the numerical results by corrected VLEACH. A simplified solution to predict the migration of volatile organic chemical due to the gas density effect has shown that a high source concentration may lead to significant downward advective gas-phase transport in a soil with a high air-permeability.     

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.     

Application of in situ biosparging to remediate a petroleum-hydrocarbon spill site: field and microbial evaluation

In this study, a full-scale biosparging investigation was conducted at a petroleum-hydrocarbon spill site. Field results reveal that natural attenuation was the main cause of the decrease in major contaminants [benzene, toluene, ethylbenzene, and xylenes (BTEX)] concentrations in groundwater before the operation of biosparging system. Evidence of the occurrence of natural attenuation within the BTEX plume includes: (1) decrease of DO, nitrate, sulfate, and redox potential, (2) production of dissolved ferrous iron, sulfide, methane, and CO(2), (3) decreased BTEX concentrations along the transport path, (4) increased microbial populations, and (5) limited spreading of the BTEX plume. Field results also reveal that the operation of biosparging caused the shifting of anaerobic conditions inside the plume to aerobic conditions. This variation can be confirmed by the following field observations inside the plume due to the biosparging process: (1) increase in DO, redox potential, nitrate, and sulfate, (2) decrease dissolved ferrous iron, sulfide, and methane, (3) increased total cultivable heterotrophs, and (4) decreased total cultivable anaerobes as well as methanogens. Results of polymerase chain reaction, denaturing gradient gel electrophoresis, and nucleotide sequence analysis reveal that three BTEX biodegraders (Candidauts magnetobacterium, Flavobacteriales bacterium, and Bacteroidetes bacterium) might exist at this site. Results show that more than 70% of BTEX has been removed through the biosparging system within a 10-month remedial period at an averaged groundwater temperature of 18 degrees C. This indicates that biosparging is a promising technology to remediate BTEX contaminated groundwater.