Influence of mass transfer characteristics for DNAPL source depletion and contaminant flux in a highly characterized glaciofluvial aquifer

The transfer of contaminant mass between the nonaqueous- and aqueous-phases is a process of central importance for the remediation of sites contaminated by dense nonaqueous-phase liquids (DNAPLs). This paper describes a comparison of the results obtained with various alternative DNAPL-aqueous-phase mass transfer models contained in the literature for predicting DNAPL source-zone depletion times in groundwater systems. These dissolution models were largely developed through laboratory column experiments. To gain insight into the implications of various representations of the local-scale kinetic as well as equilibrium DNAPL dissolution processes, aquifer heterogeneity and the complex architecture of a DNAPL source-zone, the aqueous-phase contaminant concentrations and mass fluxes arriving at a down-gradient compliance boundary are analyzed in a conditional stochastic framework. The hydrogeologic setting is a heterogeneous fluvial aquifer in Southwest Germany, referred to as the aquifer analog dataset, that was intensively characterized in three dimensions for hydrogeological parameters that include permeability, effective porosity, grain size, mineralogy and sorption coefficients. By embedding the various dissolution models into the compositional, multiphase flow model, CompFlow, the relative times predicted for complete depletion of a released DNAPL source due to natural dissolution are explored. Issues related to achieving environmental benefits through, for example, partial DNAPL-zone source removal via enhanced remedial technologies are also discussed. In this context, performance metrics in the form of peak aqueous-phase contaminant concentrations and mass fluxes arriving at a down-gradient compliance boundary are compared to each other. This is done for each of the alternative mass transfer models. A significant reduction in the fractional flux at a downstream location from the DNAPL source can be achieved by partial source-zone mass reduction; however, peak concentration levels at the same location remain much higher than the United States Environment Protection Agency (US-EPA) drinking water limits. Although groundwater quality was found to improve more rapidly for the equilibrium dissolution model, it is also shown that dissolution models that promote rapid DNAPL disappearance produce greater prediction uncertainty in the aqueous-phase flux reduction.     

A robust approach for iterative contaminant source location and release history recovery

Contamination source identification is a crucial step in environmental remediation. The exact contaminant source locations and release histories are often unknown due to lack of records and therefore must be identified through inversion. Coupled source location and release history identification is a complex nonlinear optimization problem. Existing strategies for contaminant source identification have important practical limitations. In many studies, analytical solutions for point sources are used; the problem is often formulated and solved via nonlinear optimization; and model uncertainty is seldom considered. In practice, model uncertainty can be significant because of the uncertainty in model structure and parameters, and the error in numerical solutions. An inaccurate model can lead to erroneous inversion of contaminant sources. In this work, a constrained robust least squares (CRLS) estimator is combined with a branch-and-bound global optimization solver for iteratively identifying source release histories and source locations. CRLS is used for source release history recovery and the global optimization solver is used for location search. CRLS is a robust estimator that was developed to incorporate directly a modeler's prior knowledge of model uncertainty and measurement error. The robustness of CRLS is essential for systems that are ill-conditioned. Because of this decoupling, the total solution time can be reduced significantly. Our numerical experiments show that the combination of CRLS with the global optimization solver achieved better performance than the combination of a non-robust estimator, i.e., the nonnegative least squares (NNLS) method, with the same solver.     

Analytical solutions of contaminant transport in homogeneous and isotropic aquifer in three-dimensional groundwater flow

Environmental Science and Pollution Research - Modeling three-dimensional contaminant transport released from arbitrary shape source geometries is useful in hydrological and environmental sciences....     

Mineralogical compositions of aquifer matrix as necessary initial conditions in reactive contaminant transport models

Mineralogical compositions and their spatial distributions are important initial conditions for reactive transport modeling. However, popular Kd-based "reactive" transport models only require contaminant concentrations in the pore fluids as initial conditions, and minerals implicitly represent infinite sources and sinks in these models. That situation results in a general neglect of mineralogical characterization in site investigations. This study uses a coupled multi-component reactive mass transport model to predict the natural attenuation of a ground water plume at a uranium mill tailings site in western USA. Numerous ground water geochemistry data are available at this site, but mineralogical data are sketchy. Even given the well-defined pore fluid chemistry, variations of secondary mineral species and mineral abundances in the aquifer resulted in significantly different modeling outcomes. Results show that the amount of calcite in the aquifer determines the distances of plume migration. The possible presence of jurbanite, an aluminum sulfate phase, can store acidity temporarily but cause more severe contamination on a later date. The surfaces of iron oxyhydroxides can store significant amounts of sulfate and protons and serve as a second source for prolonged contamination. These simulations under field conditions illustrate that mineralogical compositions are an essential requirement for accurate prediction of contaminant fate and transport.     

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.     

Heuristic space–time design of monitoring wells for contaminant plume characterization in stochastic flow fields

An optimization methodology for designing groundwater quality monitoring networks applicable to stochastic flow fields is presented and evaluated. The approach sets itself apart from previous techniques by incorporating the time dimension directly into the objective function. This function is extremized using a directed partial enumeration strategy guided by physical considerations related to transport processes. The result is a set of monitoring well locations and a sampling schedule that minimizes plume characterization error while satisfying constraints on the maximum number of wells and allowable number of active wells. The method is evaluated using hypothetical plumes with varying degrees of heterogeneity. Results indicate that the proposed approach is successful in generating near-optimal sampling networks that satisfy all imposed constraints. Monitoring networks with as little as three active wells and a total of 12 wells are found to provide adequate plume characterization for low toxicity contaminants.     

Denitrification and phenol degradation in a contaminated aquifer

A natural groundwater system modified by pollutant phenols and agricultural nitrate has been modelled in the laboratory by a series of sacrificial microcosm experiments. Samples of aquifer sediment and groundwater from the margin of the phenol plume were used to inoculate anaerobic microcosms enriched in nitrate and pollutant phenols. Rapid degradation of phenol and p-cresol was observed over a 35-day period leading to the generation of inorganic carbon and a number of transient intermediates. O-cresol proved to be recalcitrant on the experimental time-scale. A mass balance calculation shows that, during degradation, carbon was conserved in the aqueous phase. Groundwater-sediment interactions were monitored using carbon stable isotope data. A mass balance for solution TIC indicates thatp-cresol degradation stimulated the dissolution of sedimentary carbonate phases due to the formation of carbonic acid. Compound-specific carbon isotope analysis (GC-IRMS) was used to search for 13C enrichment in residual p-cresol. A slight enrichment trend (epsilon = -2.5/1000) was tentatively identified. The potential of this fractionation effect for obtaining in situ degradation rates is discussed. Results from the microcosm experiments help to explain the observed distribution of nitrate and phenols within the polluted aquifer.     

Photochemical oxidation of reduced sulfur compounds in an urban location based on short time monitoring data

This study examines the oxidation of reduced sulfur compounds (RSCs) in urban ambient air. The photochemical conversions of RSC (such as DMS, CS₂, H₂S, DMDS, and CH₃SH) to a further oxidized form (e.g., SO₂, MSA, and H₂SO₄) were assessed using a photochemical box model. For our model simulation of RSC oxidation, measurements were taken at an urban monitoring station in Seoul, Korea (37.6° N, 127° E) during three separate time periods (e.g., Sept. 17–18, Oct. 23, and Oct. 27–28, 2003). The results indicate that DMS and H₂S were the dominant RSCs with concentrations of 370 ± 140 and 110 ± 60 pptv, respectively. The photochemical conversion of DMDS to SO₂ was found to occur more efficiently than other RSCs. The overall results of our study suggest that photochemical conversion of RSCs accounted for less than 15% of the observed SO₂ during the measurement period. The SO₂ production from DMS oxidation (mainly by the reaction with OH) was found to be affected primarily by the abstraction channel due to high NO_x levels during the experimental conditions.     

Comparative study of microbial dechlorination of chlorinated ethenes in an aquifer and a clayey aquitard

In order to determine whether natural attenuation of chlorinated ethenes by microbial activity occurs in aquitards, sediments at a site contaminated with tetrachloroethene were vertically studied by drilling. The distribution of microbes (Dehalococcoides group and anaerobic hydrogen producers) and the ability of the sediments to sustain microbial dechlorination were determined in an aquitard as well as in an aquifer. Close-spaced sampling revealed the existence of large populations of Dehalococcoides and H(2)-producing bacteria, especially in the organic-rich clayey aquitard rather than in the aquifer. The vinyl chloride reductase gene was also detected in the clay layer. Furthermore, incubation experiments indicated that the clay sediment could sustain transformations of tetrachloroethene at least to vinyl chloride. In contrast, no significant transformation was observed in the aquifer sand. Our results indicate that dechlorination of tetrachloroethene by bacteria can take place in an organic-rich clayey aquitard, and that organic-rich clay may also be important in the natural attenuation in an adjacent aquifer, possibly supplying a carbon source or an electron donor.     

Effects of a reactive barrier and aquifer geology on metal distribution and mobility in a mine drainage impacted aquifer

The Nickel Rim aquifer has been impacted for five decades by a metal-rich plume generated from the Nickel Rim mine tailings impoundment. Metals released by the oxidation of pyrrhotite in the unsaturated zone of the tailings migrate into the downgradient aquifer, affecting both the groundwater and the aquifer solids. A reactive barrier has been installed in the aquifer to remove sulfate and metals from the groundwater. The effect of the reactive barrier on metal concentrations in the aquifer solids has not previously been studied. In this study, a series of selective extraction procedures was applied to cores of aquifer sediment, to ascertain the distribution of metals among various solid phases present in the aquifer. Extraction results were combined with groundwater chemistry, geochemical modelling and solid-phase microanalyses, to assess the potential mobility of metals under changing geochemical conditions. Reactions within the reactive barrier caused an increase in the solid-phase carbonate content downgradient from the barrier. The concentrations of poorly crystalline, oxidized phases of Mn and Fe, as well as concentrations of Cr(III) associated with oxidized Fe, and poorly crystalline Zn, are lower downgradient from the barrier, whereas total solid-phase metal concentrations remain constant. Iron and Mn accumulate as oxidized, easily extractable forms in a peat layer overlying the aquifer. Although these oxides may buffer reducing plumes, they also have the potential to release metals to the groundwater, should a reduced condition be imposed on the aquifer by remedial actions.     

Anthropogenic contaminants as tracers in an urbanizing karst aquifer

Karst aquifers are uniquely vulnerable to contamination. In the Barton Springs segment of the karstic Edwards aquifer (Texas, U.S.A.), urban contaminants such as pesticides and volatile organic compounds frequently are detected in spring base flow. To determine whether contaminant concentrations change in response to storms, and if they therefore might act as tracers of focused recharge, samples were collected from Barton Springs at closely spaced intervals following three storms. Two herbicides (atrazine and simazine), two insecticides (carbaryl and diazinon), and a solvent (tetrachloroethene) described breakthrough curves over a 1-week period following one or more storms. The breakthrough curves were decomposed into two to five log-normal subcurves, which were interpreted as representing pulses of contaminants moving through the aquifer. Each subcurve could be used in the same way as an artificial tracer to determine travel time to and recovery at the spring. The contaminants have several advantages over artificial tracers: they represent the actual compounds of interest, they are injected essentially simultaneously at several points, and they are injected under those conditions when transport is of the most interest, i.e., following storms. The response of storm discharge, specific conductance, and contaminant loading at the spring depended on initial aquifer flow conditions, which varied from very low (spring discharge of 0.48 m3/s) to high (spring discharge of 2.7 m3/s): concentrations and recovery were the highest when initial aquifer flow conditions were low. This behavior provides information about aquifer structure and the influence of aquifer flow condition on transport properties.     

Influence of indoor transport and mixing time scales on the performance of sensor systems for characterizing contaminant releases

Optimizing real-time sensor systems to detect and identify relevant characteristics of an indoor contaminant event is a challenging task. The interpretation of incoming sensor data is confounded by uncertainties in building operation, in the forces driving contaminant transport, and in the physical parameters governing transport. In addition, simulation tools used by the sensor interpretation algorithm introduce modeling uncertainties. This paper explores how the time scales inherent in contaminant transport influence the information that can be extracted from real-time sensor data. In particular, we identify three time scales (within room mixing, room-to-room transport, and removal from the building) and study how they affect the ability of a Bayesian Monte Carlo (BMC) sensor interpretation algorithm to identify the release location and release mass from a set of experimental data, recorded in a multi-floor building. The research shows that some limitations in the BMC approach do not depend on details of the models or the algorithmic implementation, but rather on the physics of contaminant transport. These inherent constraints have implications for the design of sensor systems.     

Bioremediation of a diesel fuel contaminated aquifer: simulation studies in laboratory aquifer columns

The in situ bioremediation of aquifers contaminated with petroleum hydrocarbons is commonly based on the infiltration of groundwater supplemented with oxidants (e.g., O₂, NO₃⁻) and nutrients (e.g., NH₄⁺, PO₄³⁻). These additions stimulate the microbial activity in the aquifer and several field studies describing the resulting processes have been published. However, due to the heterogeneity of the subsurface and due to the limited number of observation wells usually available, these field data do not offer a sufficient spatial and temporal resolution. In this study, flow-through columns of 47-cm length equipped with 17 sampling ports were filled with homogeneously contaminated aquifer material from a diesel fuel contaminated in situ bioremediation site. The columns were operated over 96 days at 12°C with artificial groundwater supplemented with O₂, NO₃⁻ and PO₄³⁻. Concentration profiles of O₂, NO₃⁻, NO₂⁻, dissolved inorganic and organic carbon (DIC and DOC, respectively), protein, microbial cells and total residual hydrocarbons were measured. Within the first 12 cm, corresponding to a mean groundwater residence time of < 3.6 h, a steep O₂ decrease from 4.6 to < 0.3 mg l⁻¹, denitrification, a production of DIC and DOC, high microbial cell numbers and a high removal of hydrocarbons were observed. Within a distance of 24 to 40.5 cm from the infiltration, O₂ was below 0.1 mg l⁻¹ and a denitrifying activity was found. In the presence and in the absence of O₂, n-alkanes were preferentially degraded compared to branched alkanes. The results demonstrate that: (1) infiltration of aerobic groundwater into columns filled with aquifer material contaminated with hydrocarbons leads to a rapid depletion of O₂; (2) O₂ and NO₃⁻ can serve as oxidants for the mineralization of hydrocarbons; and (3) the modelling of redox processes in aquifers has to consider denitrifying activity in presence of O₂.     

Ni adsorption and Ni-Al LDH precipitation in a sandy aquifer: an experimental and mechanistic modeling study

Mining activities and industries have created nickel (Ni) contaminations in many parts of the world. The objective of this study is to increase our understanding of Ni adsorption and Nickel-Aluminium Layered Double Hydroxide (Ni-Al LDH) precipitation to reduce Ni mobility in a sandy soil aquifer. At pH ≥7.2 both adsorption and Ni-Al LDH precipitation occurred. In batch experiments with the sandy soil up to 70% of oxalate-extractable Al was taken up in LDH formation during 56 days. In a long term column experiment 99% of influent Ni was retained at pH 7.5 due to Ni adsorption (≈34%) and Ni-Al LDH precipitation (≈66%) based on mechanistic reactive transport modeling. The subsequent leaching at pH 6.5 could be largely attributed to desorption. Our results show that even in sandy aquifers with relatively low Al content, Ni-Al LDH precipitation is a promising mechanism to immobilize Ni.     

Flow and contaminant transport in an airliner cabin induced by a moving body: Model experiments and CFD predictions

The effects of a moving human body on flow and contaminant transport inside an aircraft cabin were investigated. Experiments were performed in a one-tenth scale, water-based model. The flow field and contaminant transport were measured using the Particle Image Velocimetry (PIV) and Planar Laser-Induced Fluorescence (PLIF) techniques, respectively. Measurements were obtained with (ventilation case) and without (baseline case) the cabin environmental control system (ECS). The PIV measurements show strong intermittency in the instantaneous near-wake flow. A symmetric downwash flow was observed along the vertical centerline of the moving body in the baseline case. The evolution of this flow pattern is profoundly perturbed by the flow from the ECS. Furthermore, a contaminant originating from the moving body is observed to convect to higher vertical locations in the presence of ventilation. These experimental data were used to validate a Computational Fluid Dynamic (CFD) model. The CFD model can effectively capture the characteristic flow features and contaminant transport observed in the small-scale model.     

Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms

The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 °C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O₂ concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6 ± 1.6 μg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 μg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O₂ (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O₂ consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O₂ consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O₂ did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O₂ concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O₂ concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O₂ at relatively low levels (e.g. 2–3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions.     

Pesticide transport in an aerobic aquifer with variable pH--modeling of a field scale injection experiment

Three-dimensional reactive transport simulations were undertaken to study the sorption and degradation dynamics of three herbicides in a shallow aerobic aquifer with spatially variable pH during a 216 days injection experiment. Sorption of two phenoxy acids [(+/-)-2-(4-chloro-2-methylphenoxy) propanoic acid] (MCPP) and [(+/-)-2-(2,4-dichlorophenoxy)propanoic acid] (dichlorprop) was found to be negligible. Degradation of the phenoxy acids was rapid after an initial lag phase. Degradation of the phenoxy acids could only be reproduced satisfactorily by growth-linked microbial degradation. The model fit to the field data was slightly improved if degradation was assumed to be influenced by the local pH that was observed to increase with depth ( approximately 4.5--5.7). In the observed pH-range the nitroaromatic herbicide [2-Methyl-4,6-dinitrophenol] (DNOC) was partly dissociated (pK(a)=4.31) and present in both the neutral and ionized form. The model simulations demonstrated that most of the observed spatial variation in sorption of DNOC could be explained by assuming that only the neutral form of DNOC was subject to sorption. A varying flow field was observed during the injection experiment and the model simulations documented that this most likely resulted in different migration paths for DNOC and the non-sorbing solutes. The model simulations indicated that degradation of DNOC was an important process. The degradation rate of DNOC remained constant over time and was simulated adequately by first-order kinetics. Again, the model fit to field observation was slightly improved if local pH was assumed to influence the degradation rate. Only the maximum utilization rate was estimated from the field data, while the remaining degradation parameters where successfully transferred from the laboratory study.