In situ assessment of microbial sulfate reduction in a petroleum-contaminated aquifer using push-pull tests and stable sulfur isotope analyses

Anaerobic microbial activities such as sulfate reduction are important for the degradation of petroleum hydrocarbons (PHC) in contaminated aquifers. The objective of this study was to evaluate the feasibility of single-well push-pull tests in combination with stable sulfur isotope analyses for the in situ quantification of microbial sulfate reduction. A series of push-pull tests was performed in an existing monitoring well of a PHC-contaminated aquifer in Studen (Switzerland). Sulfate transport behavior was evaluated in a first test. In three subsequent tests, we injected anoxic test solutions (up to 1000 l), which contained 0.5 mM bromide (Br-) as conservative tracer and 1 mM sulfate (SO4(2-)) as reactant. After an initial incubation period of 42.5 to 67.9 h, up to 1100 l of test solution/groundwater mixture was extracted in each test from the same location. During the extraction phases, we measured concentrations of relevant species including Br-, SO4(2-) and sulfide (S(-II)), as well as stable sulfur isotope ratios (delta 34S) of extracted, unconsumed SO4(2-) and extracted S(-II). Results indicated sulfate reduction activity in the vicinity of the test well. Computed first-order rate coefficients for sulfate reduction ranged from 0.043 +/- 0.013 to 0.130 +/- 0.015 day-1. Isotope enrichment factors (epsilon) computed from sulfur isotope fractionation of extracted, unconsumed SO4(2-) ranged from 20.2 +/- 5.5@1000 to 22.8 +/- 3.4@1000. Together with observed fractionation in extracted S(-II), isotope enrichment factors provided strong evidence for microbially mediated sulfate reduction. Thus, push-pull tests combined with stable sulfur isotope analyses proved useful for the in situ quantification of microbial sulfate reduction in a PHC-contaminated aquifer.     

Push-pull partitioning tracer tests using radon-222 to quantify non-aqueous phase liquid contamination

Naturally occurring radon in groundwater can be used as an in situ partitioning tracer for locating and quantifying non-aqueous phase liquid (NAPL) contamination in the subsurface. When combined with the single-well, push-pull test, this methodology has the potential to provide a low-cost alternative to inter-well partitioning tracer tests. During a push-pull test, a known volume of test solution (radon-free water containing a conservative tracer) is first injected ("pushed") into a well; flow is then reversed and the test solution/groundwater mixture is extracted ("pulled") from the same well. In the presence of NAPL radon transport is retarded relative to the conservative tracer. Assuming linear equilibrium partitioning, retardation factors for radon can be used to estimate NAPL saturations. The utility of this methodology was evaluated in laboratory and field settings. Laboratory push-pull tests were conducted in both non-contaminated and trichloroethene NAPL (TCE)-contaminated sediment. The methodology was then applied in wells located in non-contaminated and light non-aqueous phase liquid (LNAPL)-contaminated portions of an aquifer at a former petroleum refinery. The method of temporal moments and an approximate analytical solution to the governing transport equations were used to interpret breakthrough curves and estimate radon retardation factors; estimated retardation factors were then used to calculate TCE saturations. Numerical simulations were used to further investigate the behavior of the breakthrough curves. The laboratory and field push-pull tests demonstrated that radon retardation does occur in the presence of TCE and LNAPL and that radon retardation can be used to calculate TCE saturations. Laboratory injection-phase test results in TCE-contaminated sediment yielded radon retardation factors ranging from 1.1 to 1.5, resulting in calculated TCE saturations ranging from 0.2 to 0.9%. Laboratory extraction-phase test results in the same sediment yielded a radon retardation factor of 5.0, with a calculated TCE saturation of 6.5%. Numerical simulation breakthrough curves provided reasonably good matches to the approximate analytical solution breakthrough curves. However, non-equilibrium radon partitioning and heterogeneous TCE distributions may affect the retardation factors and TCE saturation estimates.     

Fluorescent dye imaging of the volume sampled by single well forced-gradient tracer tests evaluated in a laboratory-scale aquifer physical model

This study presents a new method to visualise forced-gradient tracer tests in 2-D using a laboratory-scale aquifer physical model. Experiments were designed to investigate the volume of aquifer sampled in vertical dipole flow tracer tests (DFTT) and push-pull tests (PPT), using a miniature monitoring well and straddle packer arrangement equipped with solute injection and recovery chambers. These tests have previously been used to estimate bulk aquifer hydraulic and transport properties for the evaluation of natural attenuation and other remediation approaches. Experiments were performed in a silica glass bead-filled box, using a fluorescent tracer (fluorescein) to deduce conservative solute transport paths. Digital images of fluorescein transport were captured under ultraviolet light and processed to analyse tracer plume geometry and obtain point-concentration breakthrough histories. Inorganic anion mixtures were also used to obtain conventional tracer breakthrough histories. Concentration data from the conservative tracer breakthrough curves was compared with the digital images and a well characterised numerical model. The results show that the peak tracer breakthrough response in dipole flow tracer tests samples a zone of aquifer close to the well screen, while the sampling volume of push-pull tests is limited by the length of the straddle packers used. The effective sampling volume of these single well forced-gradient tests in isotropic conditions can be estimated with simple equations. The experimental approach offers the opportunity to evaluate under controlled conditions the theoretical basis, design and performance of DFTTs and PPTs in porous media in relation to measured flow and transport properties.     

Evaluation of the in-situ aerobic cometabolism of chlorinated ethenes by toluene-utilizing microorganisms using push-pull tests

A series of transport, biostimulation, and activity push-pull tests were performed under induced and natural gradient conditions in a trichloroethene (TCE) and cis-dichloroethene (c-DCE) contaminated aquifer. Transport tests demonstrated the feasibility of injecting and recovering complex solute mixtures from the aquifer. During the biostimulation tests, decreases in toluene concentration and the production of o-cresol as an intermediate oxidation product indicated the presence of toluene-utilizing microorganisms. Activity tests demonstrated that the stimulated microbial community had the ability to transform injected c-DCE and trans-dichloroethene (t-DCE) at similar zero-order rates. Injected isobutene was oxidized to isobutene oxide, which indicated that a toluene ortho-monooxygenase enzyme system was likely responsible for the observed c-DCE and t-DCE transformations. c-DCE zero-order transformation rates in drift push-pull tests were similar to those obtained from traditional push-pull tests (about 0.1 microM/h). Analysis of drift test data using first-order kinetic analysis resulted in similar conclusions as those obtained using zero-order kinetic analyses. When 1-butyne, an inhibitor of toluene ortho-monooxygenase, was added to injected test solutions, the oxidation of toluene, and the transformation of isobutene, c-DCE, and t-DCE were inhibited. The results illustrate how a series of push-pull tests can be used in combination to detect, quantify and confirm in-situ cometabolic microbial transformations.     

Numerical simulations of radon as an in situ partitioning tracer for quantifying NAPL contamination using push-pull tests

Presented here is a reanalysis of results previously presented by [Davis, B.M., Istok, J.D., Semprini, L., 2002. Push-pull partitioning tracer tests using radon-222 to quantify non-aqueous phase liquid contamination. J. Contam. Hydrol. 58, 129-146] of push-pull tests using radon as a naturally occurring partitioning tracer for evaluating NAPL contamination. In a push-pull test where radon-free water and bromide are injected, the presence of NAPL is manifested in greater dispersion of the radon breakthrough curve (BTC) relative to the bromide BTC during the extraction phase as a result of radon partitioning into the NAPL. Laboratory push-pull tests in a dense or DNAPL-contaminated physical aquifer model (PAM) indicated that the previously used modeling approach resulted in an overestimation of the DNAPL (trichloroethene) saturation (S(n)). The numerical simulations presented here investigated the influence of (1) initial radon concentrations, which vary as a function of S(n), and (2) heterogeneity in S(n) distribution within the radius of influence of the push-pull test. The simulations showed that these factors influence radon BTCs and resulting estimates of S(n). A revised method of interpreting radon BTCs is presented here, which takes into account initial radon concentrations and uses non-normalized radon BTCs. This revised method produces greater radon BTC sensitivity at small values of S(n) and was used to re-analyze the results from the PAM push-pull tests reported by Davis et al. The re-analysis resulted in a more accurate estimate of S(n) (1.8%) compared with the previously estimated value (7.4%). The revised method was then applied to results from a push-pull test conducted in a light or LNAPL-contaminated aquifer at a field site, resulting in a more accurate estimate of S(n) (4.1%) compared with a previously estimated value (13.6%). The revised method improves upon the efficacy of the radon push-pull test to estimate NAPL saturations. A limitation of the revised method is that 'background' radon concentrations from a non-contaminated well in the NAPL-contaminated aquifer are needed to accurately estimate NAPL saturation. The method has potential as a means of monitoring the progress of NAPL remediation.     

Nitrate-consuming processes in a petroleum-contaminated aquifer quantified using push-pull tests combined with 15N isotope and acetylene-inhibition methods

Nitrate consumption in aquifers may result from several biogenic and abiotic processes such as denitrification, assimilatory NO3- reduction, dissimilatory NO3- reduction to ammonium (DNRA), or abiotic NO3- (or NO2-) reduction. The objectives of this study were to investigate the fate of NO3- in a petroleum-contaminated aquifer, and to assess the feasibility of using single-well push-pull tests (PPTs) in combination with 15N isotope and C2H2 inhibition methods for the quantification of processes contributing to NO3- consumption. Three consecutive PPTs were performed in a monitoring well of a heating oil-contaminated aquifer in Erlen, Switzerland. For each test, we injected 500 l of test solution containing 0.5 mM Br- as conservative tracer and either 0.5 mM unlabeled NO3- or approximately 0.3 mM 15N-labeled NO3- as reactant. Test solutions were sparged during preparation and injection with either N2, Ar or 10% C2H2 in Ar. After an initial incubation period of 1.5-3.2 h, we extracted the test solution/groundwater mixtures from the same location and measured concentrations of relevant species including Br-, NO3-, NO2-, N2O, N2, and NH4+. In addition, we determined the 15N contents of N2, N2O, NH4+, and suspended biomass from 15N/14N isotope-ratio measurements. Average total test duration was 50.5 h. First-order rate coefficients (k) were computed from measured NO3- consumption, N2-15N production and N2O-15N production. From measured NO3- consumption we obtained nearly identical estimates of k for all PPTs with small 95% confidence intervals, indicating good reproducibility and accuracy for the tests. Estimates of k from N2-15N production and N2O-15N production indicated that denitrification accounted for only 46-49% of observed NO3- consumption. Production of N2-15N in the presence of C2H2 was observed during one of the tests, which may be an indicator for abiotic NO3- reduction. Moreover, 15N isotope analyses confirmed occurrence of assimilatory NO3- reduction (0.58 at.% 15N in suspended biomass) and to a smaller extent DNRA (up to 4 at.% 15N in NH4+). Our results indicated that the combination of PPTs, 15N-isotope and C2H2 inhibition methods provided improved information on denitrification as well as alternative fates of NO3- in this aquifer.     

Combined use of field and laboratory testing to predict preferred flow paths in an heterogeneous aquifer

Elevated nitrate concentrations within a municipal water supply aquifer led to pilot testing of a field-scale, in situ denitrification technology based on carbon substrate injections. In advance of the pilot test, detailed characterization of the site was undertaken. The aquifer consisted of complex, discontinuous and interstratified silt, sand and gravel units, similar to other well studied aquifers of glaciofluvial origin, 15-40 m deep. Laboratory and field tests, including a conservative tracer test, a pumping test, a borehole flowmeter test, grain-size analysis of drill cuttings and core material, and permeameter testing performed on core samples, were performed on the most productive depth range (27-40 m), and the results were compared. The velocity profiles derived from the tracer tests served as the basis for comparison with other methods. The spatial variation in K, based on grain-size analysis, using the Hazen method, were poorly correlated with the breakthrough data. Trends in relative hydraulic conductivity (K/K(avg)) from permeameter testing compared somewhat better. However, the trends in transient drawdown with depth, measured in multilevel sampling points, corresponded particularly well with those of solute mass flux. Estimates of absolute K, based on standard pumping test analysis of the multilevel drawdown data, were inversely correlated with the tracer test data. The inverse nature of the correlation was attributed to assumptions in the transient drawdown packages that were inconsistent with the variable diffusivities encountered at the scale of the measurements. Collectively, the data showed that despite a relatively low variability in K within the aquifer under study (within a factor of 3), water and solute mass fluxes were concentrated in discrete intervals that could be targeted for later bioremediation.     

Quantifying RDX biodegradation in groundwater using δ15N isotope analysis

Isotope analysis was used to examine the extent of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegradation in groundwater along a ca. 1.35-km contamination plume. Biodegradation was proposed as a natural attenuating remediation method for the contaminated aquifer. By isotope analysis of RDX, the extent of biodegradation was found to reach up to 99.5% of the initial mass at a distance of 1.15–1.35 km down gradient from the contamination sources. A range of first-order biodegradation rates was calculated based on the degradation extents, with average half-life values ranging between 4.4 and 12.8 years for RDX biodegradation in the upper 15 m of the aquifer, assuming purely aerobic biodegradation, and between 10.9 and 31.2 years, assuming purely anaerobic biodegradation. Based on the geochemical data, an aerobic biodegradation pathway was suggested as the dominant attenuation process at the site. The calculated biodegradation rate was correlated with depth, showing decreasing degradation rates in deeper groundwater layers. Exceptionally low first-order kinetic constants were found in a borehole penetrating the bottom of the aquifer, with half life ranging between 85.0 to 161.5 years, assuming purely aerobic biodegradation, and between 207.5 and 394.3 years, assuming purely anaerobic biodegradation.The study showed that stable isotope fractionation analysis is a suitable tool to detect biodegradation of RDX in the environment. Our findings clearly indicated that RDX is naturally biodegraded in the contaminated aquifer. To the best of our knowledge, this is the first reported use of RDX isotope analysis to quantify its biodegradation in contaminated aquifers.     

Filtration and transport of Bacillus subtilis spores and the F-RNA phage MS2 in a coarse alluvial gravel aquifer: implications in the estimation of setback distances

Filtration of Bacillus subtilis spores and the F-RNA phage MS2 (MS2) on a field scale in a coarse alluvial gravel aquifer was evaluated from the authors' previously published data. An advection-dispersion model that is coupled with first-order attachment kinetics was used in this study to interpret microbial concentration vs. time breakthrough curves (BTC) at sampling wells. Based on attachment rates (katt) that were determined by applying the model to the breakthrough data, filter factors (f) were calculated and compared with f values estimated from the slopes of log (cmax/co) vs. distance plots. These two independent approaches resulted in nearly identical filter factors, suggesting that both approaches are useful in determining reductions in microbial concentrations over transport distance. Applying the graphic approach to analyse spatial data, we have also estimated the f values for different aquifers using information provided by some other published field studies. The results show that values of f, in units of log (cmax/co) m(-1), are consistently in the order of 10(-2) for clean coarse gravel aquifers, 10(-3) for contaminated coarse gravel aquifers, and generally 10(-1) for sandy fine gravel aquifers and river and coastal sand aquifers. For each aquifer category, the f values for bacteriophages and bacteria are in the same order-of-magnitude. The f values estimated in this study indicate that for every one-log reduction in microbial concentration in groundwater, it requires a few tens of meters of travel in clean coarse gravel aquifers, but a few hundreds of meters in contaminated coarse gravel aquifers. In contrast, a one-log reduction generally only requires a few meters of travel in sandy fine gravel aquifers and sand aquifers. Considering the highest concentration in human effluent is in the order of 10(4) pfu/l for enteroviruses and 10(6) cfu/100 ml for faecal coliform bacteria, a 7-log reduction in microbial concentration would comply with the drinking water standards for the downgradient wells under natural gradient conditions. Based on the results of this study, a 7-log reduction would require 125-280 m travel in clean coarse gravel aquifers, 1.7-3.9 km travel in contaminated coarse gravel aquifers, 33-61 m travel in clean sandy fine gravel aquifers, 33-129 m travel in contaminated sandy fine gravel aquifers, and 37-44 m travel in contaminated river and coastal sand aquifers. These recommended setback distances are for a worst-case scenario, assuming direct discharge of raw effluent into the saturated zone of an aquifer. Filtration theory was applied to calculate collision efficiency (alpha) from model-derived attachment rates (katt), and the results are compared with those reported in the literature. The calculated alpha values vary by two orders-of-magnitude, depending on whether collision efficiency is estimated from the effective particle size (d10) or the mean particle size (d50). Collision efficiency values for MS-2 are similar to those previously reported in the literature (e.g. ) [DeBorde, D.C., Woessner, W.W., Kiley, QT., Ball, P., 1999. Rapid transport of viruses in a floodplain aquifer. Water Res. 33 (10), 2229-2238]. However, the collision efficiency values calculated for Bacillus subtilis spores were unrealistic, suggesting that filtration theory is not appropriate for theoretically estimating filtration capacity for poorly sorted coarse gravel aquifer media. This is not surprising, as filtration theory was developed for uniform sand filters and does not consider particle size distribution. Thus, we do not recommend the use of filtration theory to estimate the filter factor or setback distances. Either of the methods applied in this work (BTC or concentration vs. distance analyses), which takes into account aquifer heterogeneities and site-specific conditions, appear to be most useful in determining filter factors and setback distances.     

Use of tracer tests to evaluate the impact of enhanced-solubilization flushing on in-situ biodegradation

Tracer tests were conducted to evaluate the effect of a complexing sugar flush (CSF) on in-situ biodegradation potential at a site contaminated by jet fuel, solvents, and other organic compounds. Technical-grade hydroxypropyl-beta-cyclodextrin was used during the CSF study, which was conducted in a hydraulically isolated cell emplaced in a surficial aquifer. In-situ biodegradation potential was assessed with the use of tracer tests, which were conducted prior to and immediately following the CSF study. Ethanol, hexanol, and benzoate were used as the biodegradable tracers, while bromide was used as a nonreactive tracer. The results indicate that the biodegradation of benzoate was similar for both tracer tests. Conversely, the biodegradation of ethanol (23% increase) and hexanol (41% increase) was greater for the post-CSF tracer test. In addition, analysis of core samples collected from within the test cell indicates that the population density of aerobic jet-fuel degraders increased in the vicinity of the injection wells during the CSF. These results indicate that the cyclodextrin flush did not deleteriously affect the indigenous microbial community. This study illustrates that tracer tests can be used to evaluate the impact of remediation activities on in-situ biodegradation potential.     

A multi-directional tracer test in the fractured Chalk aquifer of E. Yorkshire, UK

A multi-borehole radial tracer test has been conducted in the confined Chalk aquifer of E. Yorkshire, UK. Three different tracer dyes were injected into three injection boreholes and a central borehole, 25 m from the injection boreholes, was pumped at 330 m(3)/d for 8 days. The breakthrough curves show that initial breakthrough and peak times were fairly similar for all dyes but that recoveries varied markedly from 9 to 57%. The breakthrough curves show a steep rise to a peak and long tail, typical of dual porosity aquifers. The breakthrough curves were simulated using a 1D dual porosity model. Model input parameters were constrained to acceptable ranges determined from estimations of matrix porosity and diffusion coefficient, fracture spacing, initial breakthrough times and bulk transmissivity of the aquifer. The model gave equivalent hydraulic apertures for fractures in the range 363-384 microm, dispersivities of 1 to 5 m and matrix block sizes of 6 to 9 cm. Modelling suggests that matrix block size is the primary controlling parameter for solute transport in the aquifer, particularly for recovery. The observed breakthrough curves suggest results from single injection-borehole tracer tests in the Chalk may give initial breakthrough and peak times reasonably representative of the aquifer but that recovery is highly variable and sensitive to injection and abstraction borehole location. Consideration of aquifer heterogeneity suggests that high recoveries may be indicative of a high flow pathway adjacent, but not necessarily connected, to the injection and abstraction boreholes whereas low recoveries may indicate more distributed flow through many fractures of similar aperture.     

Estimating spatially-variable first-order rate constants in groundwater reactive transport systems

Numerical reactive transport models are often used as tools to assess aquifers contaminated with reactive groundwater solutes as well as investigating mitigation scenarios. The ability to accurately simulate the fate and transport of solutes, however, is often impeded by a lack of information regarding the parameters that define chemical reactions. In this study, we employ a steady-state Ensemble Kalman Filter (EnKF), a data assimilation algorithm, to provide improved estimates of a spatially-variable first-order rate constant λ through assimilation of solute concentration measurement data into reactive transport simulation results. The methodology is applied in a steady-state, synthetic aquifer system in which a contaminant is leached to the saturated zone and undergoes first-order decay. Multiple sources of uncertainty are investigated, including hydraulic conductivity of the aquifer and the statistical parameters that define the spatial structure of the parameter field. For the latter scenario, an iterative method is employed to identify the statistical mean of λ of the reference system. Results from all simulations show that the filter scheme is successful in conditioning the λ ensemble to the reference λ field. Sensitivity analyses demonstrate that the estimation of the λ values is dependent on the number of concentration measurements assimilated, the locations from which the measurement data are collected, the error assigned to the measurement values, and the correlation length of the λ fields.     

Biodegradation and mineral weathering controls on bulk electrical conductivity in a shallow hydrocarbon contaminated aquifer

Geochemical and stable carbon isotope data from closely spaced vertical intervals in a hydrocarbon-impacted aquifer were used to assess the relationship between biodegradation, mineral weathering, and enhanced bulk conductivity zones. The results show that depth zones of enhanced bulk conductivity in the contaminated aquifer had higher total dissolved solids (TDS) compared to background groundwater. The higher TDS in contaminated groundwater were due to elevated ion concentrations from enhanced mineral weathering. Depth intervals with higher concentrations of major cations overlapped with zones with higher total petroleum hydrocarbons, which were the same zones where reduction of nitrate, iron, manganese, sulfate, and methanogenesis was occurring. Hence, the zones of higher bulk conductivity may be explained by mineral weathering related to hydrocarbon biodegradation. Our results suggest that biodegradation of hydrocarbons may impart changes to the aquifer geochemistry that can be indirectly observed using geophysical techniques. We therefore argue for inclusion of geophysical investigations as part of natural attenuation assessment programs.     

Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions (epsilon=-3 per thousand) and some anaerobic studies on microbial degradation of aromatic hydrocarbons (epsilon=-1.7 per thousand) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents (epsilon=between -5 per thousand and -30 per thousand). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.     

Multi tracer test for the implementation of enhanced in-situ bioremediation at a BTEX-contaminated megasite

At the Centre for Environmental Research Leipzig-Halle (UFZ) research site in Zeitz, Germany, benzene contaminates the lower of two aquifers with concentrations of up to 20 mg/l. Since the benzene plume has a minimum length of approximately 1 km, enhanced natural attenuation measures are being considered as a remediation strategy. This study describes the performance and evaluation of a multi-species reactive tracer test using the tracers fluorescein and bromide as conservative tracers and toluene as reactive tracer. Sampling was performed over a period of six months using a detailed network of multilevel sampling wells. Toluene was only slightly retarded in comparison to bromide, whereas fluorescein was retarded considerably stronger. Therefore, it was not possible to use fluorescein as an in situ tracer for the determination of groundwater velocities. The ionic nature of fluorescein is assumed to be the major reason for its retardation. The results show that the infiltration conditions were suitable to produce a wide spreading of the tracer front along the full thickness of the aquifer. Thus, a large aquifer volume can be treated in future enhanced bioremediation measures. The total quantity of infiltrated toluene (24 l) was degraded under sulfate-reducing conditions over a flow path of 50 m. Benzylsuccinate was identified as a metabolite of toluene degradation under sulfate-reducing conditions at this site. The modelling results show that toluene degradation was described more accurately using Monod kinetics than first-order kinetics. Since toluene was only slightly retarded in comparison to bromide, sorption and desorption processes were considered to be negligible.     

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

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.     

3-D numerical evaluation of density effects on tracer tests

In this paper we present numerical simulations carried out to assess the importance of density-dependent flow on tracer plume development. The scenario considered in the study is characterized by a short-term tracer injection phase into a fully penetrating well and a natural hydraulic gradient. The scenario is thought to be typical for tracer tests conducted in the field. Using a reference case as a starting point, different model parameters were changed in order to determine their importance to density effects. The study is based on a three-dimensional model domain. Results were interpreted using concentration contours and a first moment analysis. Tracer injections of 0.036 kg per meter of saturated aquifer thickness do not cause significant density effects assuming hydraulic gradients of at least 0.1%. Higher tracer input masses, as used for geoelectrical investigations, may lead to buoyancy-induced flow in the early phase of a tracer test which in turn impacts further plume development. This also holds true for shallow aquifers. Results of simulations with different tracer injection rates and durations imply that the tracer input scenario has a negligible effect on density flow. Employing model cases with different realizations of a log conductivity random field, it could be shown that small variations of hydraulic conductivity in the vicinity of the tracer injection well have a major control on the local tracer distribution but do not mask effects of buoyancy-induced flow.     

3-D numerical evaluation of density effects on tracer tests

In this paper we present numerical simulations carried out to assess the importance of density-dependent flow on tracer plume development. The scenario considered in the study is characterized by a short-term tracer injection phase into a fully penetrating well and a natural hydraulic gradient. The scenario is thought to be typical for tracer tests conducted in the field. Using a reference case as a starting point, different model parameters were changed in order to determine their importance to density effects. The study is based on a three-dimensional model domain. Results were interpreted using concentration contours and a first moment analysis. Tracer injections of 0.036 kg per meter of saturated aquifer thickness do not cause significant density effects assuming hydraulic gradients of at least 0.1%. Higher tracer input masses, as used for geoelectrical investigations, may lead to buoyancy-induced flow in the early phase of a tracer test which in turn impacts further plume development. This also holds true for shallow aquifers. Results of simulations with different tracer injection rates and durations imply that the tracer input scenario has a negligible effect on density flow. Employing model cases with different realizations of a log conductivity random field, it could be shown that small variations of hydraulic conductivity in the vicinity of the tracer injection well have a major control on the local tracer distribution but do not mask effects of buoyancy-induced flow.     

A controlled field experiment on groundwater contamination by a multicomponent DNAPL: creation of the emplaced-source and overview of dissolved plume development

A unique field experiment has been undertaken at the CFB Borden research site to investigate the development of dissolved chlorinated solvent plumes from a residual dense non-aqueous phase liquid (DNAPL) source. The "emplaced-source" tracer test methodology involved a controlled emplacement of a block-shaped source of sand containing chlorinated solvents below the water table. The gradual dissolution of this residual DNAPL solvent source under natural aquifer conditions caused dissolved solvent plumes of trichloromethane (TCM), trichloroethene (TCE) and perchloroethene (PCE) to continuously develop down gradient. Source dissolution and 3-D plume development were successfully monitored via 173 multilevel samplers over a 475-day tracer test period prior to site remediation research being initiated. Detailed groundwater level and hydraulic conductivity data were collected. Development of plumes with concentrations spanning 1-700,000 micrograms/1 is described and key processes controlling their migration identified. Plumes were observed to be narrow due to the weakness of transverse dispersion processes and long due to advection and significant longitudinal dispersion, very limited sorptive retardation and negligible, if any, attenuation due to biodegradation or abiotic reaction. TCM was shown to be essentially conservative, TCE very nearly conservative and PCE, consistent with its greater hydrophobicity, more retarded yet having a greater mobility than observed in previous Borden field tests. The absence of biodegradation was ascribed to the prevailing aerobic conditions and lack of any additional biodegradable carbon substrates. The transient groundwater flow regime caused significant transverse lateral plume movement, plume asymmetry and was likely responsible for most of the, albeit limited, transverse horizontal plume spreading. In agreement with the widespread incidence of extensive TCE and PCE plumes throughout the industrialized world, the experiment indicates such solvent plumes are likely to be highly mobile and persistent, at least in aquifers that are aerobic and have low sorption potential (low foc content).