Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

Effect of long-term changes in soil chemistry induced by road salt applications on N-transformations in roadside soils

Of several impacts of road salting on roadside soils, the potential disruption of the nitrogen cycle has been largely ignored. Therefore the fates of low-level ammonium-N and nitrate-N inputs to roadside soils impacted by salting over an extended period (decades) in the field have been studied. The use of road salts disrupts the proportional contributions of nitrate-N and ammonium-N to the mineral inorganic fraction of roadside soils. It is highly probable that the degree of salt exposure of the soil, in the longer term, controls the rates of key microbial N transformation processes, primarily by increasing soil pH. Additional influxes of ammonium-N to salt-impacted soils are rapidly nitrified therefore and, thereafter, increased leaching of nitrate-N to the local waterways occurs, which has particular relevance to the Water Framework Directive. The results reported are important when assessing the fate of inputs of ammonia to soils from atmospheric pollution.     

Natural attenuation of chlorinated ethene compounds: model development and field-scale application at the Dover site

A multi-dimensional and multi-species reactive transport model was developed to aid in the analysis of natural attenuation design at chlorinated solvent sites. The model can simulate several simultaneously occurring attenuation processes including aerobic and anaerobic biological degradation processes. The developed model was applied to analyze field-scale transport and biodegradation processes occurring at the Area-6 site in Dover Air Force Base, Delaware. The model was calibrated to field data collected at this site. The calibrated model reproduced the general groundwater flow patterns, and also, it successfully recreated the observed distribution of tetrachloroethene (PCE), trichloroethene (TCE), dichloroethylene (DCE), vinyl chloride (VC) and chloride plumes. Field-scale decay rates of these contaminant plumes were also estimated. The decay rates are within the range of values that were previously estimated based on lab-scale microcosm and field-scale transect analyses. Model simulation results indicated that the anaerobic degradation rate of TCE, source loading rate, and groundwater transport rate are the important model parameters. Sensitivity analysis of the model indicated that the shape and extent of the predicted TCE plume is most sensitive to transmissivity values. The total mass of the predicted TCE plume is most sensitive to TCE anaerobic degradation rates. The numerical model developed in this study is a useful engineering tool for integrating field-scale natural attenuation data within a rational modeling framework. The model results can be used for quantifying the relative importance of various simultaneously occurring natural attenuation processes.     

Use of principal component analysis to profile temporal and spatial variations of chlorinated solvent concentration in groundwater

This work aims at evaluating spatial distribution patterns of concentration variations for chlorinated solvents in groundwater, based on principal component analysis and geographic information system (GIS) tools. The study investigates long-time series of chlorinated solvent concentrations in groundwater measured for 18 contaminated industrial sites. The characterization of contaminant plumes and delineation of pollutant sources are essential for choosing appropriate monitoring and remediation strategies, as contaminated groundwaters are characterized by complex patterns of spatial and temporal concentration variability, with wide unpredictable fluctuations over time. The present work describes the results of a new exploratory statistical method called the Variability Index Method (VIM) applied to environmental data to assess the performance of using concentration variations as molecular tracers to reveal aquifer dynamics, industrial impacts, and point sources for contamination plumes. The application of this method provides a useful assessment of controls over contaminant concentration variations as well as support for remediation techniques.     

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.     

Choice of dispersion coefficients in reactive transport calculations on smoothed fields

Local dispersion dominates the mixing of compounds that are introduced separately into the subsurface and do not partition into any other than the aqueous phase. Thus, reactions between these compounds are controlled by dispersive mixing if they are not limited by kinetics. I quantify longitudinal dispersive mixing by the longitudinal effective dispersion coefficient of a conservative tracer introduced by a point-like injection [Water Resour. Res. 36 (12) (2000) 3591-3604]. In the upscaling of mixing-controlled reactive transport, I apply the mean velocity and the effective dispersion coefficient to the macroscopic transport calculations, whereas the reactive parameters on the macro-scale are identical to those on the local scale. The applicability of the approach is demonstrated for the transport of compounds undergoing a second-order irreversible bimolecular reaction. Ten realizations of a two-dimensional heterogeneous log-conductivity field are considered. Using the effective dispersion parameters, the overall mass balance is met in the ensemble average, whereas solute spreading is underestimated. I assess the lack of spreading by the difference between the expected macrodispersion and effective dispersion coefficients. I extend the approach to simulations on log-conductivity fields obtained by kriging of regularly spaced conductivity measurements. These fields contain the large-scale features of the true fields but do not resolve the small-scale variability. For the calculations on the kriged fields, the corresponding conditional covariance is substituted into the analytical expressions of effective dispersion, yielding a correction effective dispersion coefficient. The comparison between simulations on the fully resolved fields and on the kriged fields indicates that the approach is valid for wide plumes meeting the ergodicity condition. The high variability of mixing on small scales unresolved by kriging, however, leads to severe uncertainty when mixing-controlled reactions are predicted for narrow plumes.     

New methodology to investigate potential contaminant mass fluxes at the stream-aquifer interface by combining integral pumping tests and streambed temperatures

The spatial pattern and magnitude of mass fluxes at the stream-aquifer interface have important implications for the fate and transport of contaminants in river basins. Integral pumping tests were performed to quantify average concentrations of chlorinated benzenes in an unconfined aquifer partially penetrated by a stream. Four pumping wells were operated simultaneously for a time period of 5 days and sampled for contaminant concentrations. Streambed temperatures were mapped at multiple depths along a 60m long stream reach to identify the spatial patterns of groundwater discharge and to quantify water fluxes at the stream-aquifer interface. The combined interpretation of the results showed average potential contaminant mass fluxes from the aquifer to the stream of 272microgm(-2)d(-1) MCB and 71microgm(-2)d(-1) DCB, respectively. This methodology combines a large-scale assessment of aquifer contamination with a high-resolution survey of groundwater discharge zones to estimate contaminant mass fluxes between aquifer and stream.     

Behaviour and fate of nine recycled water trace organics during managed aquifer recharge in an aerobic aquifer

The fate of nine trace organic compounds was evaluated during a 12month large-scale laboratory column experiment. The columns were packed with aquifer sediment and evaluated under natural aerobic and artificial anaerobic geochemical conditions, to assess the potential for natural attenuation of these compounds during aquifer passage associated with managed aquifer recharge (MAR). The nine trace organic compounds were bisphenol A (BPA), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR), carbamazepine, oxazepam, iohexol and iodipamide. In the low organic carbon content Spearwood sediment, all trace organics were non-retarded with retardation coefficients between 1.0 and 1.2, indicating that these compounds would travel at near groundwater velocities within the aquifer. The natural aerobic geochemical conditions provided a suitable environment for the rapid degradation for BPA, E2, iohexol (half life <1day). Lag-times for the start of degradation of these compounds ranged from <15 to 30days. While iodipamide was persistent under aerobic conditions, artificial reductive geochemical conditions promoted via the addition of ethanol, resulted in rapid degradation (half life <1days). Pharmaceuticals (carbamazepine and oxazepam) and disinfection by-products (NDMA and NMOR) did not degrade under either aerobic or anaerobic aquifer geochemical conditions (half life >50days). Field-based validation experiments with carbamazepine and oxazepam also showed no degradation. If persistent trace organics are present in recycled waters at concentrations in excess of their intended use, natural attenuation during aquifer passage alone may not result in extracted water meeting regulatory requirements. Additional pre treatment of the recycled water would therefore be required.     

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.     

Application of first-order reliability method to modelling the fate and transport of benzene in groundwater

Parameter uncertainty plays a significant role in decision making regarding groundwater contamination and remediation, especially for non-conservative chemicals. This paper presents a probabilistic screening model to accommodate parameter uncertainty in the aquifer media, and physical–chemical parameters, using the first-order reliability method (FORM). The application of the developed model is illustrated on transport of benzene in groundwater. The results matched those obtained using the Monte Carlo simulation method, with a smaller number of functional evaluations. Parametric studies were conducted to estimate the effect of various parameters on the results.     

Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation

A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.     

Uncertainty assessment of contaminant plume length estimates in heterogeneous aquifers

The Virtual Aquifer approach is used in this study to assess the uncertainty involved in the estimation of contaminant plume lengths in heterogeneous aquifers. Contaminant plumes in heterogeneous two-dimensional conductivity fields and subject to first order and Michaelis-Menten (MM) degradation kinetics are investigated by the center line method. First order degradation rates and plume lengths are estimated from point information obtained along the plume center line. Results from a Monte-Carlo investigation show that the estimated rate constant is highly uncertain and biased towards overly high values. Uncertainty and bias amplify with increasing heterogeneity up to maximum values of one order of magnitude. Calculated plume lengths reflect this uncertainty and bias. On average, plume lengths are estimated to about 50% of the true plume length. When plumes subject to MM degradation kinetics are investigated by using a first order rate law, an additional error is introduced and uncertainty as well as bias increase, causing plume length estimates to be less than 40% of the true length. For plumes with MM degradation kinetics, therefore, a regression approach is used which allows the determination of the MM parameters from center line data. Rate parameters are overestimated by a factor of two on average, while plume length estimates are about 80% of the true length. Plume lengths calculated using the MM parameters are thus closer to the correct length, as compared to the first order approximation. This approach is therefore recommended if field data collected along the center line of a plume give evidence of MM kinetics.     

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).     

A contaminated site investigation: comparison of information gained from geophysical measurements and hydrogeological modeling

The investigation of contaminated sites is usually a long and expensive process. It is therefore desirable to use a combination of methodologies in an integrative approach that can reduce redundant information gathering. The objective of this study was to examine the usefulness of 2 non-intrusive exploration techniques in a contaminated site investigation. Borehole positioning based on geophysical measurements was compared to positioning based on the Bayesian expert system for flow-field modeling. The goal set at the field site was the assessment of the type and load of contaminants transported from the landfill site to the adjacent aquifer and the extent of leachate plumes within the groundwater. The two methods made different demands on information gathering and were found to be complementary. The geophysical approach focused attention on the waste compartments at the site and on mixing plumes in the adjacent aquifer but could not, without prior information, provided information on the flow field. The Bayesian approach to flow-field modeling determined areas of greatest model uncertainty at the model boundaries. The model highlighted areas of greatest uncertainty that might otherwise have been overlooked and provided information on the most likely mean direction of the leachate plumes. It was concluded that both methods contribute to a site investigation and should be used before additional drilling is carried out.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Numerical experiments and field results on the size of steady state plumes

Contaminated groundwater poses a serious risk for drinking water supplies. Under certain conditions, however, groundwater contamination remains restricted to a tolerable extent because of natural attenuation processes. We present an innovative approach to evaluate the size of these so-called steady-state plumes by 2-D and 1-D modelling in homogeneous aquifers. If longitudinal mixing is negligible, scenarios can be modelled in a simplified way using a 1-D domain vertical to the direction of flow. We analysed the sensitivity of the plume length with respect to biodegradation kinetics, flow velocity, transverse vertical dispersivity alphat, the source and aquifer geometry and reaction stoichiometry. Our findings indicate that for many readily biodegradable compounds transverse-dispersive mixing rather than reaction kinetics is the limiting factor for natural attenuation. Therefore, if alphat, aquifer and source geometry and concentrations of electron acceptors and donors are known, the length of the steady state contaminant plume can be predicted. The approach is validated under field conditions for an ammonium plume at a former landfill site in SW Germany.     

Extent and causes of 3D spatial variations in potential N mineralization and the risk of ammonium and nitrate leaching from an N-impacted permanent grassland near York, UK

Changes in the dynamics of inorganic N species transformations with depth have been investigated for seven soil profiles from a nitrogen-impacted ancient grassland on a nature reserve outside York in the UK, using incubation experiments. In five of the profiles, both ammonification and nitrification are occurring below the rooting zone, probably partly in response to the low C:N ratio in the soils. This contributes to elevated nitrate concentrations found in an adjacent stream. Accumulation of ammonium during incubation in the sub-soils of these five profiles suggests a high probability of ammonium leaching down the profiles as ammonium inputs and outputs at a given depth approach equilibrium. This ammonium may also be nitrified at depth. However, in the two profiles with the most acidic surface horizons, net mineralization was negligible or negative; some initial ammonium-N and ammonium-N produced during incubation were nitrified, so the loss in ammonium-N was closely balanced by nitrate-N production.     

Role of back diffusion and biodegradation reactions in sustaining an MTBE/TBA plume in alluvial media

A methyl tert-butyl ether (MTBE) / tert-butyl alcohol (TBA) plume originating from a gasoline spill in late 1994 at Vandenberg Air Force Base (VAFB) persisted for over 15 years within 200 feet of the original spill source. The plume persisted until 2010 despite excavation of the tanks and piping within months after the spill and excavations of additional contaminated sediments from the source area in 2007 and 2008. The probable history of MTBE concentrations along the plume centerline at its source was estimated using a wide variety of available information, including published details about the original spill, excavations and monitoring by VAFB consultants, and our own research data. Two-dimensional reactive transport simulations of MTBE along the plume centerline were conducted for a 20-year period following the spill. These analyses suggest that MTBE diffused from the thin anaerobic aquifer into the adjacent anaerobic silts and transformed to TBA in both aquifer and silt layers. The model reproduces the observation that after 2004 TBA was the dominant solute, diffusing back out of the silts into the aquifer and sustaining plume concentrations much longer than would have been the case in the absence of such diffusive exchange. Simulations also suggest that aerobic degradation of MTBE or TBA at the water table in the overlying silt layer significantly affected concentrations of MTBE and TBA by limiting the chemical mass available for back diffusion to the aquifer.     

In situ biodegradation determined by carbon isotope fractionation of aromatic hydrocarbons in an anaerobic landfill leachate plume (Vejen,Denmark)

Concentrations and isotopic compositions (13C/12C) of aromatic hydrocarbons were determined in eight samples obtained from the strongly anoxic part of the leachate plume downgradient from the Vejen Landfill (Denmark), where methanogenic, sulfate-reducing and iron-reducing conditions were observed. Despite the heterogeneous distribution of the compounds in the plume, the isotope fractionation proved that ethylbenzene and m/p-xylene were subject to significant biodegradation within the strongly anoxic plume. The isotope fractionation factors (alphaC) for the degradation of the m/p-xylene (1.0015) and ethylbenzene (1.0021) obtained from the field observations were similar to factors previously determined for the anaerobic degradation of toluene and o-xylene in laboratory experiments, and suggest that in situ biodegradation is one major process controlling the fate of these contaminants in this aquifer. The isotope fractionation determined for 1,2,4-trimethylbenzene and 2-ethyltoluene suggested in situ biodegradation; however, the isotopic composition did not correlate well with the respective concentration as expressed by the Rayleigh equation. Some other compounds (1,2,3-trimethylbenzene, o-xylene, naphthalene and fenchone) did not show significant enrichments in delta13C values along the flow path. The compound concentrations were too low for accurate isotope analyses of benzene, toluene, 1- and 2-methylnaphthalene, while interferences in the chromatography made it impossible to evaluate the isotopic composition for 4-ethyltoluene, 1,3,5-trimethylbenzene and camphor.In addition to demonstrating the potential of assessing isotopic fractionation as a means for documenting the in situ biodegradation of complex mixtures of aromatic hydrocarbons in leachate plumes, this study also illustrates the difficulties for data interpretation in complex plumes and high analytical uncertainties for isotope analysis of organic compounds in low concentration ranges.     

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.