Rapid evolution of redox processes in a petroleum hydrocarbon-contaminated aquifer

Ground water chemistry data collected over a six-year period show that the distribution of contaminants and redox processes in a shallow petroleum hydrocarbon-contaminated aquifer has changed rapidly over time. Shortly after a gasoline release occurred in 1990, high concentrations of benzene were present near the contaminant source area. In this contaminated zone, dissolved oxygen in ground water was depleted, and by 1994 Fe(III) reduction and sulfate reduction were the predominant terminal electron accepting processes. Significantly, dissolved methane was below measurable levels in 1994, indicating the absence of significant methanogenesis. By 1996, however, depletion of solid-phase Fe(III)-oxyhydrox ides in aquifer sediments and depletion of dissolved sulfate in ground water resulted in the onset of methanogenesis. Between 1996 and 2000, water-chemistry data indicated that methanogenic metabolism became increasingly prevalent. Molecular analysis of 16S-rDNA extracted from sediments shows the presence of a more diverse methanogenic community inside as opposed to outside the plume core, and is consistent with water-chemistry data indicating a shift toward methanogenesis over time. This rapid evolution of redox processes reflects several factors including the large amounts of contaminants, relatively rapid ground water flow (approximately 0.3 m/day [approximately foot/day]), and low concentrations of microbially reducible Fe(III) oxyhydroxides ( approximately 1 micromol/g) initially present in aquifer sediments. These results illustrate that, under certain hydrologic conditions, redox conditions in petroleum hydrocarbon-contaminated aquifers can change rapidly in time and space, and that the availability of solid-phase Fe(III)-oxyhydroxides affects this rate of change.     

Groundwater,salt and contaminant transport in a coastal aquifer system with a low-permeability layer in the intertidal zone

Low-permeability layer (LPL), formed by natural deposit or artificial reclamation and commonly found below the intertidal zone of coastal groundwater system, can retard the ingress of seawater and contaminants, and shorten the travel time of the land-sourced contaminant to the marine environment compared with a homogenous sandy coastal aquifer. However, there is limited understanding on how an intertidal LPL, a condition occurred in a coastal aquifer at Moreton Bay, Australia, influences the groundwater and contaminant transport across the shallow beach aquifer system. We characterized the aquifer hydrological parameters, monitored the in situ groundwater heads, and constructed a 2-D numerical model to analyses the cross-shore hydrological processes in this stratified system. The calibrated model suggests that in the lower aquifer, the inland-source fresh groundwater flowed horizontally towards the sea, upwelled along the freshwater–saltwater interface, and exited the aquifer at the shore below the LPL. Whereas in the upper aquifer, the tidally driven seawater circulation formed a barrier that prevented fresh groundwater from horizontal transport and discharge to the beach above the LPL, thereby directing its leakage to the lower aquifer. A contaminant represented by a conservative tracer was ‘released’ the upper aquifer in the model and results showed that the spreading extent of the contaminant plume, the maximum rate of contaminant discharge to the ocean, and its plume length decreased compared with a simulation case in a homogenous sandy aquifer. Sensitivity analysis was also conducted to investigate the characteristics of the LPL, including its continuity and hydraulic conductivity, which were found to vary along the beach at Moreton Bay. The result shows that with a lower hydraulic conductivity and continuous layer of LPL reduced the groundwater exchange and contaminant transport between upper and lower aquifer. The findings from the combined field and modelling investigations on the impact of an intertidal LPL on coastal aquifer systems highlight its significant implications to alter the groundwater and mass transport across the land–ocean interface.     

Multicomponent simulations of contrasting redox environments at an LNAPL site

A two-dimensional multicomponent reactive transport modeling approach was used to simulate contaminant transport and the evolution of redox processes at a large-scale kerosene-contaminated site near Berlin, Germany. In contrast to previous site-scale modeling studies that focused either on one or two contaminants or on steady-state redox conditions, multiple contaminants and electron acceptors, including mineral phase Iron (III), were considered with an evolving redox zonation. Inhibition terms were used to switch between the different electron acceptor processes in the reaction scheme. The transient evolution of redox zones and contaminant plumes was simulated for two separate transects of the site, which have different geology and ground water recharge distributions and where quite different downstream contaminant and terminal electron–accepting process (TEAP) distributions are observed. The same reaction system, calibrated to measured concentrations along one of the transects, was used in both cases, achieving a reasonable match with observed concentrations. The differences between the two transects could thus to some extent be attributed to the different hydrological and hydrogeological conditions, in particular ground water recharge distributions. Long-term simulations showed that the distribution of TEAPs evolves as Fe(III) becomes depleted, with conditions becoming increasingly methanogenic, leading to changes in contaminant plume lengths. The models were applied to assess the potential effects of planned changes in land use at the site that may affect the ground water recharge distribution. The simulated redox zonation responded strongly to changes in recharge, which in turn led to changes in the contaminant plume lengths.     

Attenuation of a Mixed Chromium and Chlorinated Etjeme Ground Wate Plume in Estuarine Influenced Glaciated Sediments

The natural attenuation behavior of a ground water contaminant plume containing chromium and chlorinated ethenes in glaciated sediments was assessed using traditional and nontraditional methods. The mixed waste is transported through and attenuated within an estuarine influenced ground water aquifer of spatially varying redox character and organic carbon content. Contaminant fate and speciation were assessed as a function of geochemical conditions. Total, speciation-based, and sequential chemical extraction analyses were performed to determine contaminant partitioning and the redox capacity of the aquifer. Chromium speciation and partitioning were correlated with the reductive capacity and redox conditions of the aquifer sediments spatially distributed within the aquifer. Reductive dechlorination and partitioning of chlorinated ethenes were correlated with the organic carbon content and redox conditions of the aquifer sediments. The data showed that sharp redox gradients existed within the aquifer. Active reduction and retardation of both chromium and chlorinated ethenes was exhibited. The aqueous hexavalent chromium concentrations decreased to near nondetect levels in the vicinity of the receptor, whereas degradation products of higher-order chlorinated ethenes increased as a fraction of the total chlorinated ethene concentrations along the length of the plume. The potential for competition for reducing power under specific cases within the aquifer was suggested by the data, highlighting the need to include contaminant interactions in natural attenuation assessments.     

Crude Oil Metabolites in Groundwater at Two Spill Sites

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil. Monitoring data from 1988 to 2015 at one of the sites located near Bemidji, MN show that the plume of metabolites is expanding toward a lakeshore located 335 m from the source zone. Other mass balance studies of the site have demonstrated that the plume expansion is driven by the combined effect of continued presence of the residual crude oil source and depletion of the electron accepting capacity of solid phase iron oxide and hydroxides on the aquifer sediments. These plumes of metabolites are not covered by regulatory monitoring and reporting requirements in Minnesota and other states. Yet, a review of toxicology studies indicates that polar metabolites of crude oil may pose a risk to aquatic and mammalian species. Together the results suggest that at sites where residual sources are present, monitoring of NVDOC may be warranted to evaluate the fates of plumes of hydrocarbon transformation products.     

Microtopographical and hydrophysical controls on subsurface flow and solute transport: A continuous solute release experiment in a subarctic bog

Resource extraction and transportation activities in subarctic Canada can result in the unintentional release of contaminants into the surrounding peatlands. In the event of a release, a thorough understanding of solute transport within the saturated zone is necessary to predict plume fate and the potential impacts on peatland ecosystems. To better characterize contaminant transport in these systems, approximately 13,000 L/day of sodium chloride tracer (200 mg/L) was released into a bog in the James Bay Lowland. The tracer was pumped into a fully penetrating well (1.5 m) between July 5 and August 18, 2015. Horizontal and vertical plume development was measured via in situ specific conductance and water table depth from an adaptive monitoring network. Over the spill period, the bulk of the plume travelled a lateral distance of 100 m in the direction of the slight regional groundwater and topographical slope. The plume shape was irregular and followed the hollows, indicating preferential flow paths due to the site microtopography. Saturated transport of the tracer occurred primarily at ~25 cm below ground surface (bgs), and at a discontinuous high hydraulic conductivity layer ~125 cm bgs due to a complex and heterogeneous vertical hydraulic conductivity profile. Plume measurement was confounded by a large amount of precipitation (233 mm over the study period) that temporarily diluted the tracer in the highly conductive upper peat layer. Longitudinal solute advection can be approximated using local water table information (i.e., depth and gradient); microtopography; and meteorological conditions. Vertical distribution of solute within the peat profile is far more complex due to the heterogeneous subsurface; characterization would be aided by a detailed understanding of the site‐specific peat profile; the degree of decomposition; and the type of contaminant (e.g., reactive/nonreactive). The results of this research highlight the difficulty of tracking a contaminant spill in bogs and provide a benchmark for the characterization of the short‐term fate of a plume in these complex systems.     

Mathematical modeling and practical verification of groundwater and contaminant transport in a chosen natural aquifer

The paper addresses the 2D mathematical equation of conservative contaminant transport in an aquifer for chosen contaminants. The contaminants (chlorides and sulfates) are subject to instantaneous reversible part of sorption process. The term of instantaneous reversible sorption in the presented equation has been described by the non-linear Freundlich adsorption isotherm, widely applied in practice in relation to static processes (for local equilibrium). The numerical solution (using the finite difference method) has been based on the previously calculated values of longitudinal and transverse dispersion coefficients and the non-linear adsorption parameters for the chosen contaminants. Based on this model, the values of chloride and sulfate concentration isolines have been calculated and compared with the measured maximal concentrations in the chosen natural aquifer (installed piezometers). Additionally, the values of chloride concentrations have been calculated taking into account the influence of radioactive decay term, using the numerical value of the firstorder decay rate constant for an adopted theoretical radionuclide.     

Assessing the Transport of Pharmaceutical Compounds in a Layered Aquifer Discharging to a Stream

A groundwater plume containing high concentrations of pharmaceutical compounds, mainly sulfonamides, barbiturates, and ethyl urethane, in addition to chlorinated ethenes and benzene was investigated. The contamination originating from a former pharmaceutical industry discharges into a multilayered aquifer system and a downgradient stream. In this study, geological and hydrogeological data were integrated into a numerical flow model to examine identified trends using statistical approaches, including principal component analysis and hierarchal cluster analysis. A joint interpretation of the groundwater flow paths and contaminant concentrations in the different compartments (i.e., groundwater and hyporheic zone) provided insight on the transport processes of the different contaminant plumes to the stream. The analysis of historical groundwater concentrations of pharmaceutical compounds at the site suggested these compounds are slowly degrading. The pharmaceutical compounds migrate in both a deep semiconfined aquifer, as well as in the shallow unconfined aquifer, and enter the stream along a 2-km stretch. This contrasted with the chlorinated ethenes, which mainly discharge to the stream as a focused plume from the unconfined aquifer. The integrated approach developed here, combining groundwater flow modeling and statistical analyses of the contaminant concentration data collected in groundwater and the hyporheic zone, lead to an improved understanding of the observed distribution of contaminants in the unconfined and semiconfined aquifers, and thus to their discharge to the stream. This approach is particularly relevant for large and long-lasting contaminant sources and plumes, such as abandoned landfills and industrial production sites, where field investigations may be very expensive.     

Enhancement of In Situ Bioremediation of BTEX-Contaminated Ground Water by Oxygen Diffusion from Silicone Tubing

A field study of oxygen-enhanced biodegradation was carried out in a sandy iron-rich ground water system contaminated with gasoline hydrocarbons. Prior to the oxygen study, intrinsic microbial biodegradation in the contaminant plume had depleted dissolved oxygen and created anaerobic conditions. An oxygen diffusion system made of silicone polymer tubing was installed in an injection well within an oxygen delivery zone containing coarse highly permeable sand. During the study, this system delivered high dissolved oxygen (DO) levels (39 mg/L) to the ground water within a part of the plume. The ground water was sampled at a series of monitors in the test zone downgradient of the delivery well to determine the effect of oxygen on dissolved BTEX, ground water geochemistry, and microbially mediated biodegradation processes. The DO levels and Eh increased markedly at distances up to 2.3 m (7.5 feet) downgradient. Potential biofouling and iron precipitation effects did not clog the well screens or porous medium. The increased dissolved oxygen enhanced the population of aerobes while the activity of anaerobic sulfate-reducing bacteria and methanogens decreased. Based on concentration changes, the estimated total rate of BTEX biodegradation rose from 872 mg/day before enhancement to 2530 mg/day after 60 days of oxygen delivery. Increased oxygen flux to the test area could account for aerobic biodegradation of 1835 mg/day of the BTEX. The estimated rates of anaerobic biodegradation processes decreased based on the flux of sulfate, iron (II), and methane. Two contaminants in the plume, benzene and ethylbenzene, are not biodegraded as readily as toluene or xylenes under anaerobic conditions. Following oxygen enhancement, however, the benzene and ethylbenzene concentrations decreased about 98%, as did toluene and total xylenes.     

Influence of a coarse interlayer on seawater intrusion and contaminant migration in coastal aquifers

Vertical 2D slice laboratory experiments were carried out in homogenous and layered sand tanks to elucidate the effects of a highly permeable (coarse‐grained sand) interlayer on seawater intrusion and transport of contaminants to a coastal sea. Tidal fluctuations produced oscillations in the seawater–freshwater transition zone, fluctuations of the contaminant infiltration rate and a zigzag contaminant plume outline. The seawater wedge became discontinuous at the (vertical) edges of the interlayer because of increased lateral movement of the seawater–freshwater interface within the interlayer. The contaminant plume formed a tail within the interlayer depending on the tidal stage, and similar to the wedge, its movement was accentuated. A simple analytical model that neglected vertical flow reliably predicted steady‐state seawater intrusion into the coastal aquifer. Numerical modeling was used to gain insight into the groundwater hydrodynamics and contaminant migration. The numerical results confirmed the experimental findings, i.e. that a highly permeable interlayer can provide a rapid transit path for contaminants to reach the seaward boundary and that the interlayer amplifies the effects of tidal fluctuations, resulting in wider transition zones for the seawater wedge and contaminant plume. Numerical simulations further showed that, with increasing interlayer hydraulic conductivity, the maximum seawater intrusion distance inside the interlayer increases approximately linearly. For the fixed‐head contaminant injection condition used, the model showed that contaminant infiltration increases approximately logarithmically with increasing interlayer hydraulic conductivity (other factors held fixed). Copyright © 2013 John Wiley & Sons, Ltd.     

Characteristics of distribution and transport of petroleum contaminants in fracture-karst water in Zibo Area, Shandong Province, China

Fracture-karst water is an important water resource for the water supply in North China. Petroleum contamination is one of the most problematic types of the groundwater pollution. The characteristics of distribution and transport of the petroleum contaminants in fracture-karst water are different from those in porous water. The flow velocity of fracture-karst water is much faster than the velocity of porous water on an average. Therefore, contaminant transport in fracture-karst water is an absolute advection-dominated problem. The plume of the petroleum contamination may extend to several kilometers from pollution sources. It was not caused by the oil pool floating on the water table but by the oil components dissolved and scattered in groundwater. The distribution of the petroleum contaminants over space are concentrated in the strong conductive zone on the plane. On the vertical section the highest concentration of the oil contaminants appeared in the strata where the contamination sources were located. The concentrations of the oil contaminants in wells changed greatly over time. Therefore, the curves of concentration versus time fluctuated greatly. The reasons are as follows. (a) Fracture-karst water has a very great velocity. (b) Local flow fields which were caused by pumping and stoppage in some wells changed frequently. (c) In fracture-karst aquifer the transport channels are complicated. (d) Residual oil in vadose zone was leached after rainfall. It is of great practical value for the control and remediation of petroleum contamination in fracture-karst aquifer to understand those characteristics.     

Simulation of a Ground Water Recirculation Well with a Dual-Column Laboratory Setup

This paper describes a dual-column laboratory setup consisting of a glass column and a stainless-steel column filled with aquifer material. The setup was used to replicate a ground water recirculation well that serves as an in situ reactor and a combined injection/withdrawal well. The treatment solution consisted of a buffered titanium (III) citrate/vitamin B₁₂ mixture. The first column, representing the well, was made of glass, allowing for visual inspection of the mixing. The stainless-steel column was instrumented with redox (Eh) probes to monitor the changes in redox conditions. The redox measurement showed that, although the sand contained large quantities of iron oxides, the oxidation rate was relatively slow and the titanium solution would remain reduced for some time in the aquifer, continuing to react with the contaminants. This laboratory setup was used to optimize the reagent concentrations and rate of delivery for field implementation. It was found that 4 mM titanium citrate and 3 mg/L vitamin B₁₂ were sufficient to degrade 1,1,2,2-tetrachloroethane and carbon tetrachloride within one day, but not trichloroethylene, which required five days with 10 mM titanium citrate and 5 mg/L vitamin B₁₂.     

Modeling and Remediation of Ground Water Contamination at the Engelse Werk Wellfield

Contaminants have been threatening the Engelse Werk wellfield located between the town of Zwolle and the IJssel River in the Netherlands. Chemical analysis of water samples taken in production wells, both at the IJssel River and near the Zwolle railway station, indicated elevated concentrations of mainly organic contaminants including benzene, bentazon, acenaftene, trichloroethane, and bromacil. Immediate contaminant prevention and remediation measures are needed to safeguard the production wells. Ground water flow and transport models were developed to assist in the design of remediation strategies. Ground water flow models indicated that the IJssel River and a waste disposal ditch at the railway station are within the capture zone of the wellfield. A chloride transport model simulated minimum travel times in the order of four to 13 years for contaminants in the IJssel River to reach the production wells of the wellfield. A transport model for benzene was set up to advise on the remediation measures to be taken at the waste disposal ditch to clean up the contamination in the upper aquifer between this site and the Engelse Werk wellfield. The designed remediation system consists of 12 pumping wells with a combined capacity of 1650 m³/day. The system is capable of reducing the benzene levels at the threatened production wells at the Engelse Werk wellfield to a permissible level below 0.1 μg/L within a period of 5 years.     

Monte Carlo evaluation of microbial-mediated contaminant reactions in heterogeneous aquifers

Monte Carlo simulations are conducted to evaluate microbial-mediated contaminant reactions in an aquifer comprised of spatially variable microbial biomass concentrations, aquifer hydraulic conductivities, and initial electron donor/acceptor concentrations. A finite element simulation model is used that incorporates advection, dispersion, and Monod kinetic expressions to describe biological processes. Comparisons between Monte Carlo simulations of heterogeneous systems and simulations using homogeneous formulation of the same two-dimensional transport problem are presented. For the assumed set of parameters, physical aquifer heterogeneity is found to have a minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system; however, it noticeably changes the dispersion, skewness, and peakness of contaminant concentration distributions. Similarly, for low microbial growth rate, given favorable microbial growth characteristics, biological heterogeneity has minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system. On the other hand, when higher effective growth rates are assumed, biological heterogeneity and spatial heterogeneities in essential electron donor/acceptors reduce the efficiency of biotic contaminant reactions; consequently, model simulations derived from heterogeneous biomass distributions predict remediation time scales that are longer than those simulated for homogeneous systems. When correlations between physical aquifer and biological heterogeneities are considered, the assumed correlation affects predicted mean and variance of contaminant concentration and biomass distributions. For example, an assumed negative correlation between hydraulic conductivity and the initial biomass distribution produces a plume where less efficient biotic contaminant reactions occur at the leading edge of the plume; this is consistent with less degradation/transformation occurring over regions of higher groundwater velocities. However, the presence and absence of these correlations do not appear to affect the efficiency of microbial-mediated contaminant attenuation.     

Ground-Water Quality at a Creosote Waste Site

An abandoned creosote facility in Conroe, Texas, has become a field site for the National Center for Ground Water Research (NCGWR) at Rice University. Ground-water contamination in the shallow aquifer beneath the site was characterized by sampling soils and water quality at 14 monitoring wells and 35 boreholes. Results from six sampling trips over two years for inorganic and organic chemical concentrations in the ground water show wells around the site were contaminated to levels above 800 μg/l for naphthalene, 400 μg/1 for methyl naphthalene, and 150 μg/1 for dibenzofuran. Conservative constituents, traced by chloride concentrations up to 75 mg/l, have migrated 300 ft (90 m) downgradient of the site. Organic contaminants have been adsorbed and microbially degraded in their migration from the waste source as evidenced by their attenuated concentrations. Detailed field pump tests have been performed to evaluate hydraulic conductivity at several of the shallow wells. The U.S. Geological Survey (USGS) Solute Transport Model (Konikow and Bredehoeft, 1978) has been used to predict chloride plume patterns and evaluate parameters which govern transport processes at the Conroe waste site.     

A kinetic approach for simulating redox‐controlled fringe and core biodegradation processes in groundwater: model development and application to a landfill site in Piedmont,Italy

A three‐dimensional model for predicting redox controlled, multi‐species reactive transport processes in groundwater systems is presented. The model equations were fully integrated within a MODFLOW‐family reactive transport code, RT3D. The model can simulate organic compound biodegradation coupled to different terminal electron acceptor processes. A computational approach, which uses the spatial and temporal distribution of the rates of different redox reactions, is proposed to map redox zones. The method allows one to quantify and visualize the biological degradation reactions occurring in three distinct patterns involving fringe, pseudo‐core and core processes. The capabilities of the numerical model are demonstrated using two hypothetical examples: a batch problem and a simplified two‐dimensional reactive transport problem. The model is then applied to an unconfined aquifer underlying a leaking landfill located near the city of Turin, in Piedmont (Italy). At this site, high organic load from the landfill leachate activates different biogeochemical processes, including aerobic degradation, denitrification, manganese reduction, iron reduction, sulfate reduction and methanogenesis. The model was able to describe and quantify these complex biogeochemical processes. The proposed model offers a rational framework for simulating coupled reactive transport processes occurring beneath a landfill site. Copyright © 2008 John Wiley & Sons, Ltd.     

A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Lessons learned from a suite of CFB Borden experiments

This article summarizes several of many field-based studies of subsurface contaminant transport conducted over the last 30 years at the Canadian Forces Base (CFB) Borden site. The field research initially consisted of extensive monitoring of a leachate plume from an abandoned landfill and its analytical and numerical modeling. Lessons learned from these initial studies led to the execution and interpretation of a variety of tracer tests involving conservative and reactive/organic solutes tests performed at various scales. The lessons learned from these tracer tests revealed a number of deficiencies in classical theories of contaminant dispersion and reaction processes as they occur in groundwater, and thus spawned a new era of process-oriented research within the hydrogeological community. The extensively monitored tracer tests were followed by controlled spills of organic contaminants to observe their subsurface movement and distribution as well as the emplacement of a variety of contaminant sources in the saturated and unsaturated zones to study the ambient transport of contaminants. The controlled spills and emplaced sources of various contaminants were then utilized for testing various active and passive remediation technologies. These studies have led to fundamental insights and lessons learned that have significantly contributed to research on contaminant transport in both the saturated and unsaturated zones. Over the years, data generated by the University of Waterloo (UW) researchers and their collaborators continues to be examined by various research groups and has led to additional new insights on subsurface transport of various chemicals.     

Effect of variable‐density groundwater flow on nitrate flux to coastal waters

A two‐dimensional variable‐density groundwater flow and transport model was developed to provide a conceptual understanding of past and future conditions of nitrate (NO₃) transport and estimate groundwater nitrate flux to the Gulf of Mexico. Simulation results show that contaminant discharge to the coast decreases as the extent of saltwater intrusion increases. Other natural and/or artificial surface waters such as navigation channels may serve as major sinks for contaminant loading and act to alter expected transport pathways discharging contaminants to other areas. Concentrations of NO₃ in the saturated zone were estimated to range between 30 and 160 mg?L^?1 as NO₃. Relatively high hydraulic vertical gradients and mixing likely play a significant role in the transport processes, enhancing dilution and contaminant migration to depth. Residence times of NO₃ in the deeper aquifers vary from 100 (locally) to about 300 years through the investigated aquifer system. NO₃ mass fluxes from the shallow aquifers (0 to 5.7 × 10⁴ mg?m^?2?day^?1) were primarily directed towards the navigation channel, which intersects and captures a portion of the shallow groundwater flow/discharge. Direct NO₃ discharge to the sea (i.e. Gulf of Mexico) from the shallow aquifer was very low (0 to 9.0 × 10¹ mg · m^?2?day^?1) compared with discharge from the deeper aquifer system (0 to 8.2 × 10³ mg?m^?2?day^?1). Both model‐calibrated and radiocarbon tracer‐determined contaminant flux estimates reveal similar discharge trends, validating the use of the model for density‐dependent flow conditions. The modelling approach shows promise to evaluate contaminant and nutrient loading for similar coastal regions worldwide. Copyright © 2015 John Wiley & Sons, Ltd.     

Bioattenuation in groundwater impacted by landfill leachate traced with δ13C

The impact on groundwater imparted by the infiltration of high dissolved organic carbon (DOC) leachate from capped, unlined landfills can be attenuated by biogeochemical reactions beyond the waste source, although such reactive loss in the aquifer is difficult to distinguish from conservative advective dispersion. Compound-specific measurement of δ(13)C in carbon species, including CH(4), dissolved inorganic carbon (DIC), and the major DOC compounds (acetate, humic acid, and fulvic acid) provides a constraint in this assessment that can assist in exercises of modeling and prediction of leachate transport. The Trail Road municipal landfill near Ottawa, Ontario, Canada, hosts an unlined sector which produces a highly enriched leachate (DOC >4500 mg/L) that provides a good site to examine reactive attenuation within the receptor aquifer. Acetate, a sentinel component of leachate DOC (~1000 mg C/L), is absent in impacted groundwater. Mass balance calculations together with reaction modeling suggest continued acetate fermentation with calcite control on DIC and δ(13)C(DIC) evolution. In groundwater within 50 m of the landfill, methane concentrations are elevated (~10 mg/L), consistent with acetate fermentation, whereas δ(13)C(CH4) measurements in deeper groundwater range down to -51‰ compared with -60‰ in the landfill demonstrating oxidative loss. DOC in the deep aquifer is remarkably depleted to values less than -40‰ suggesting methanotrophic bacteria selectively consume isotopically light CH(4) to fix carbon. Continued reaction of leachate DOC in groundwater is demonstrated by evolution away from conservative mixing lines on diagrams of δ(13)C vs. concentrations of DIC and DOC.