Groundwater Contaminant Plume Research Articles

Unravelling the influence of heterogeneities and abstraction on groundwater flow and solute transport in a fractured carbonate aquifer, Sicily, Italy

The migration of a groundwater contaminant plume consisting of light nonaqueous phase liquids (LNAPLs) along the Ionian coastline of Sicily, Italy, has been reported to follow a trajectory that is inconsistent with the regional hydraulic gradient. The influence of several faults affecting the fractured carbonate bedrock aquifer, and groundwater abstraction from a well, were hypothesized to be responsible for the anomalous trajectory of the contaminant plume. A conceptual hydrogeological model was developed for the study area that incorporated structural information derived from geophysical surveys and the mapping of fractures in bedrock outcrops. This conceptual model was incorporated into numerical groundwater flow and solute transport models to simulate the groundwater transport of the light nonaqueous phase liquids. Four model scenarios representing different levels of complexity were tested to assess the relative influence of geological heterogeneity and groundwater abstraction on the migration of the contaminant plume. Results show that underground major discontinuity systems, invoking the presence of the faults in the model domain accounted for the observed migration of the contaminant plume, act as conduits for groundwater flow. Conversely, groundwater abstraction from a well was found to result in relatively minor, localized impacts to the migration of the contamination plume. This study demonstrates the importance of incorporating geological heterogeneity into groundwater modelling and environmental risk assessments associated with the storage of LNAPLs.

Laboratory-scale characterization of slow-release permanganate gel (SRP-G) for the in-situ treatment of chlorinated-solvent groundwater plumes

Significant challenges remain for the remediation of chlorinated-solvent plumes in groundwater, such as trichloroethene (TCE) and tetrachloroethene (PCE). A novel slow-release permanganate gel (SRP-G) technique may show promise for the in-situ treatment (remediation) of chlorinated contaminant plumes in groundwater. A series of laboratory experiments were conducted to characterize the primary physical factors that influence SRP-G gelation processes to optimize SRP-G performance for plume treatment. Specifically, experiments were conducted to quantify gel zeta potential, particle size distribution, and viscosity to determine SRP-G gelation characteristics and processes. These experiments tested various concentrations of two SRP-G amendment solutions (NaMnO4 and KMnO4) prepared with 30-wt.% and 50-wt.% colloidal silica to determine such influences on zeta potential, particle size distribution, and viscosity. The results of this study show that SRP-G solutions with low zeta potential and relatively high pH favor more rapid SRP-G gelation. The concomitant interaction of the predominantly negatively charged colloidal silica particles and the positively charged dissociated cations (Na+ and K+) in the SRP-G solution had the effect of stabilizing charge imbalance via attraction of particles and thereby inducing a greater influence on the gelation process. Gel particle size distribution and changes in viscosity had a significant influence on SRP-G solution gelation. The addition of permanganate (NaMnO4 or KMnO4) increased the average particle size distribution and the viscosity of the SRP-G solution and decreased the overall gelation time. SRP-G amendments (NaMnO4 or KMnO4) prepared with 50-wt.% colloidal silica showed more effective gelation (and reduced gelation time) compared to SRP-G amendments prepared with 30-wt.% colloidal silica. Under the conditions of these experiments, it was determined that both the 7-wt.% NaMnO4 solution and 90 mg/L KMnO4 solution using 50-wt.% colloidal silica would be the optimal injection SRP-G solution concentrations for this in-situ treatment technique.

Multi-technological integration in a smelting site: Visualizing pollution characteristics and migration pattern

Heavy metal(loid)s pollution of industrial legacies has become a severe environmental issue worldwide. Linking soil pollution to groundwater contaminant plumes would make invisible pollution features visible across the site, but related studies are lacking and require the convergence of multiple technologies. This study uniformly managed the soil and groundwater data in a 3D visualization model to pellucidly assess the spatial distribution of critical contaminants beyond simple drilling information. The distribution of Pb, Zn, As, and Cd in soil-groundwater system has a strong correlation to historical production, substance type, soil property, and groundwater flow direction. Over 2600 measurements of High-density electrical resistivity tomography (ERT) data were used to guarantee the exactness of soil structures. Hydraulic conductivity showed a strongest correlation (R2 = 0.86), yielding a calibrated model to reveal the anisotropic and contaminant transport in the region, with the consequent minimize the drilling tests. This study provides a template for the description of a verifiable scenario of hydrogeological conditions and pollution characteristics at smelting sites, coupled with traditional exploration and non-invasive techniques. The findings highlight the significance of visualizing the internal state of the soil-groundwater system under consideration, thus providing a basis for targeted control measures against site contamination.

Multizone Aquatic Ecological Exposures to Landfill Contaminants from a Groundwater Plume Discharging to a Pond.

While it is recognized that groundwater contaminant plumes can impact surface waters, there remains little information on the magnitude, spatial extent, and especially temporal variability of the resulting exposure to the variety of aquatic organisms, particularly for stagnant surface waters (e.g., ponds). The present study of a historic landfill plume discharging to a pond investigated contaminant exposure to multiple aquatic zones (endobenthic, epibenthic, pelagic) over approximately 1 year within a temperate climate. Landfill tracers included the artificial sweetener saccharin, ammonium, chloride, and specific conductance. Sampling of pond sediment porewater (upwelling groundwater) and continuous geophysical imaging of the subsurface showed a relatively stable plume footprint covering approximately 26% of the pond, although with spatially varying leachate composition, revealing year-round exposure to endobenthic (within sediments) organisms. Substantial and variable contaminant exposure to epibenthic organisms within the plume footprint was shown by elevated specific conductance measured directly above the sediment interface. Exposure varied daily at times and increased through winter to values representing undiluted plume groundwater. Exposure to pelagic organisms (overlying water) covered a larger area (~50%) due to in-pond circulation. The stream outlet concentrations were stable at approximately 10 times dilution for chloride and saccharin, but were substantially less in summer for ammonium due to in-pond processes. Whereas groundwater contaminants are typically assumed elevated at base flows, the outlet stream contaminant mass discharges to downstream receptors were notably higher in winter than summer, following stream flow patterns. Insights from the present study into the timings and locations of contaminant plume exposure to multiple ecological zones of a pond can provide guidance to contaminated site and aquatic ecosystem managers on improved monitoring, assessment, and remediation protocols. Environ Toxicol Chem 2023;42:1667-1684. © 2023 His Majesty the King in Right of Canada and The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

Uptake of Per- and Polyfluoroalkyl Substances by Fish, Mussel, and Passive Samplers in Mobile-Laboratory Exposures Using Groundwater from a Contamination Plume at a Historical Fire Training Area, Cape Cod, Massachusetts.

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L-1 in reference groundwater and 6100 to 15,000 ng L-1 in contaminated groundwater. Biotic concentration factors (CFb) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg-1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CFb generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CFb between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CFb = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CFb, and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Solution of the backward problem for the space-time fractional diffusion equation related to the release history of a groundwater contaminant

Abstract Finding the history of a groundwater contaminant plume from final measurements is an ill-posed problem and, consequently, its solution is extremely sensitive to errors in the input data. In this paper, we study this problem mathematically. So, firstly, existence and uniqueness theorems of a quasi-solution in an appropriate class of admissible initial data are given. Secondly, in order to overcome the ill-posedness of the problem and also approximate the quasi-solution, two approaches (computational and iterative algorithms) are provided. In the computational algorithm, the finite element method and TSVD regularization are applied. This method is tested by two numerical examples. The results reveal the efficiency and applicability of the proposed method. Also, in order to construct the iterative methods, an explicit formula for the gradient of the cost functional J is given. This result helps us to construct two iterative methods, i.e., the conjugate gradient algorithm and Landweber iteration algorithm. We prove the Lipschitz continuity of the gradient of the cost functional, monotonicity and convergence of the iterative methods. At the end of the paper, a numerical example is given to show the validation of the iterative algorithms.

Assessments of radiological and toxicological risks from the use of groundwater and surface water in the zone of influence of the uranium production legacy site

Radioactive and chemical contamination of groundwater and surface water (Konoplyanka and Dnipro Rivers) in the zone of influence of the soviet era uranium production legacy site - Prydniprovsky Chemical Plant (PChP, Kamianske) is a source of radiological and toxicological risks for the population. Modeled water use scenarios included drinking water consumption, crop irrigation, fishing, and usage of the river beaches for recreation. According to the assessment results, the radiological risks of water usage in current conditions are low. At the same time, a conservative assessment indicates potential future toxicological risks from uranium (use of groundwater for drinking) and from manganese (due to accumulation in river fish). In the long term, risks from groundwater may increase significantly due to the dispersion of contaminated groundwater plumes outside the industrial site, or due to unrestricted access of the population to the territory of the PChP. To reduce uncertainty in the risk assessment results, it is important to improve the groundwater monitoring network downstream from the PChP site and to collect site-specific data on manganese transfer coefficients to fish.

PFAS exposures in Veneto, Italy: the role of biomonitoring in addressing a serious public health threat

Background and Aim In 2013, high levels of perfluoroalkyl substances (PFAS) were identified in the drinking water of the Veneto region, Italy, primarily due to industrial emissions from a nearby PFAS manufacturer. For decades, the factory released wastewater into the ground, contaminating both surface water bodies and groundwater, mainly by perfluorooctanoic acid (PFOA), before charcoal filters were introduced. The groundwater contamination plume extends over 190 km2 and reached public waterworks serving 30 municipalities (roughly 130,000 inhabitants). This presentation will provide an overview of the Veneto health surveillance program and its impact. Methods The health surveillance program started in January 2017 and continues for the prevention, early diagnosis and treatment of chronic disorders possibly associated with PFAS. The target population included 105,000 residents of the contaminated area born between 1951 and 2014. Data are collected through a structured interview on socio-demographic characteristics, personal health history and lifestyle habits; routine blood and urine tests; and the measurements of 12 PFAS. The population is being recruited for a second round, which started in September 2020. Results By February 2022 55,597 individuals were recruited (60,5% of invited) in the 1st round, and 2,623 in the 2nd round. The PFAS with the highest serum concentrations was PFOA (median 36.8 ng/mL), about 20 times higher than in the Italian population with background exposures, followed by perfluorooctanesulfonic acid (PFOS) (median 3.8 ng/mL) and perfluorohexanesulfonic acid (PFHxS) (median 3.7 ng/mL). Conclusions This population is unique in that biomonitoring has been offered to the entire highly exposed population. The program includes a thorough assessment of individual exposure as well as behavioural and clinical risk factors for cardiometabolic disorders, providing tailored counselling for exposure and risk reduction, and the referral of subjects with altered biomarkers for subsequent diagnostic and therapeutic evaluation. Keywords: PFAS, biomonitoring, health surveillance program, PFOA contamination

A new analytical model for transport of multiple contaminants considering remediation of both NAPL source and downgradient contaminant plume in groundwater

The contamination of groundwater aquifers by chlorinated solvents is a water-resource issue of great importance worldwide. Such contaminants are difficult to treat because they are often released as dense non-aqueous phase liquids (DNAPLs). Research shows that the application of remediation technologies to both the NAPL source and dissolved plume can lead to more efficient remediation, rather than to either alone. In these remediation efforts, analytical models that evaluate behavior and fate of contaminants do provide a better understanding of the performance of these remedial technologies. To the best of our knowledge, there exist no analytical model of simulating the plume migration of multiple contaminants with capabilities of accounting for both NAPL source and plume remediation simultaneously and different retardation for original chlorinated solvent contaminant and its degradation byproducts. In this study, we present a new analytical model for remediating both NAPL source and downgradient contaminant plume in groundwater at sites contaminated with chlorinated solvents and their degradation products with different retardation factors as well as considering both NAPL source and plume remediation simultaneously. A source model that accounts for the depletion of mass by the processes of dissolution or first-order decay reactions, corresponding with the removal or destruction of the source mass, is coupled to a plume reactive transport model. The source model is accounted for by relating source mass to the flux-averaged source discharge concentration through a power function. The developed analytical model considers 1-D advection, 3-D dispersion, first-order decay reactions and ingrowth as well as linear isothermal equilibrium sorption. The proposed analytical solution was derived through successive application of the Laplace transform in time and the double finite Fourier cosine transform regarding y and z. The correctness of the analytical model and its auxiliary FORTRAN computer program code are proved by showing excellent agreements between the simulated plume concentrations of all contaminants obtained from the derived analytical model and from a semi-analytical model available in the literature. Application of the proposed analytical solutions illustrates that the use of identical retardation factors for all contaminants may lead to underestimation or overestimation of the mobility of the contaminants, in cases when the retardation factors of the individual contaminants are greatly different from the identical retardation factor value adopted in all contaminants. From the experiments on six scenarios corresponding six remedial treatments, we found out that both the enhanced source decay and partial removal of source mass are main controlling factors at reducing the concentrations of all the contaminants, whereas plume decay leads to effective reduction in the concentrations of PCE, however, rather it causes unfavorable increases of the concentrations of the degradation byproducts.Ultimately, the developed model is used to better understand the impacts of various possible combinations of remedial efforts and management decisions on remediation of the subsurface contamination and quantify the benefit of a certain remediation decision.

Anthropogenic and Geogenic Mercury in Surface Waters in the Mature Bathurst Mining Camp, New Brunswick, Canada

Abstract Interactions between a cyanide leach used for Au extraction and cinnabar-bearing gossan tailings at the Murray Brook mine have led to the development of an Hg-enriched contaminated groundwater plume that discharges to the nearby Gossan Creek. Naturally occurring cinnabar in the area poses a challenge in distinguishing mining-related contamination from background Hg concentrations. Surface water data from throughout the Bathurst Mining Camp was used to establish interelement relationships compared to pH and the spatial distributions of Hg, SO42−, Cl, Cu, NO3−, Zn, Pb, and Ca/HCO3− values. Statistical significance of anomalous measurements was evaluated to assess geogenic versus anthropogenic contributions of mining associated elements. Watershed analysis indicated that the Murray Brook tailings facility may sit on a basinal divide with potential for tailings leachate-impacted groundwater and surface water migration toward the northeast as well as northwest toward Gossan Creek. Elevated NO3− was detected in two streams south-west of Gossan Creek alongside greater than normal Hg concentrations. Other locations in the study area away from the Murray Brook area show little geochemical evidence for impact of mining on surface waters despite Hg concentrations as high as 0.019 µg L-1. Points with geogenic Hg concentration on the order of 0.01 µg L-1 were observed throughout the study area, particularly in the Upsalquitch River tributaries south-west of Gossan Creek and in the surface waterbodies west of the Restigouche deposit, indicating weathering of cinnabar-bearing gossan.

Forecasting Groundwater Contaminant Plume Development Using Statistical and Machine Learning Methods

AbstractForecasting groundwater contaminant plume development is critical for determining risks to downgradient receptors and predicting the time to site closure. However, accurate forecasts are a formidable challenge due to the complexities of a heterogeneous subsurface. While historically groundwater well data in combination with numerical flow models have been used for this task, the advent of machine learning offers new data‐driven opportunities for improving contaminant fate and transport predictions. In this study, we interrogate the viability of two forecasting models—Prophet and damped Holt's exponential smoothing model—for predicting groundwater contaminant plume development. The impacts of spatial and temporal data density on the accuracy of the forecasts are evaluated. For wells with declining contaminant concentrations, the damped Holt's method achieves more accurate forecasts. However, only Prophet allows for the inclusion of exogenous regressors, enabling predictions of future declining trends in wells with still increasing contaminant concentrations. Application of these models does not only require robust training data, but also an understanding of model biases. Overall, powerful data‐driven models are already available for contaminant plume prediction, but groundwater sampling approaches will have to improve, for instance, through the collection of real‐time spatial and temporal high‐resolution data, to take full advantage of their capabilities.

Health Risk Assessment for the Residential Area Adjacent to a Former Chemical Plant.

A health risk assessment was carried out for the residents of Łęgnowo-Wieś settlement adjacent to a former Zachem Chemical Plant, Bydgoszcz, Poland. Due to the unique Zachem site history and contamination profile, an innovative strategy for soil sampling and contaminant selection was applied. The novelty in the developed strategy consisted of selecting substances for the health risk assessment, taking into consideration the location and boundaries of the groundwater contamination plumes in relation to contamination sources. This allowed limiting the number of the analysed contaminants. The risk assessment focused on the surface soil of a residential area, which was divided into 20 sampling sectors and 6 backyards with wells from which water was used for watering edible plants. A total of 80 inorganic and organic substances were determined, including metals, phenol, aniline, BTEX, diphenyl sulphone, chloroaniline, epichlorohydrin, hydroxybiphenyl, nitrobenzene, octylphenols, toluenediamine, toluidine, 16 polycyclic aromatic hydrocarbons, tetrachloroethylene and trichloroethylene. For the health risk assessment, the United States Environmental Protection Agency’s deterministic method was applied. This applies conservative assumptions to obtain risk estimates protective for most of the potential receptors. Three exposure pathways were analysed: (1) incidental soil ingestion, (2) dermal contact with soil and (3) inhalation of fugitive soil particles and volatiles. In all sampling sectors and backyards, the total non-cancer risks (hazard index) were significantly lower than the acceptable level of 1. The acceptable cancer risk level for the single carcinogen of 1 × 10−5 was only insignificantly exceeded in the case of benzo(a)pyrene in three sectors and one backyard. The total cancer risks were lower than the acceptable level of 1 × 10−4 in all sampling sectors and all backyards. The findings show that the soil in the entire residential area is safe for the residents’ health and no remedial actions are required. However, since not all possible exposure pathways were analysed in this study, further research focused on assessing the health risk resulting from the consumption of locally grown food is strongly recommended.

A pilot study characterizing tetrachloroethylene exposure with exhaled breath in an impacted community

Martinsville, Indiana overlays four groundwater contamination plumes, including a U.S. Environmental Protection Agency (EPA)-designated Superfund site. The primary contaminants are tetrachloroethylene (PCE), trichloroethylene (TCE), and other volatile organic compounds (VOCs). Martinsville represents many similar communities facing the challenge of groundwater and soil contamination and vapor intrusion, where residents are often frustrated by the lack of help in understanding and addressing the problem. The objective of this study was to evaluate PCE in exhaled breath to identify and quantify exposure to PCE and to explore the extent and level of PCE exposure among community residents. We measured chlorinated VOCs in exhaled breath samples from 38 healthy individuals who lived either in a contamination area or outside any plume area. We also measured VOCs in indoor air and tap water samples collected from 10 homes. PCE was detected in all exhaled breath samples (mean: 6.6 μg/m3; range: 1.9–44 μg/m3) and tap water samples (mean: 0.74 μg/L; range: 0.39–0.92 μg/L). PCE was detected in six of nine (66%) homes with air concentrations ranging from 1.6 to 70 μg/m3, exceeding the EPA action level of 42 μg/m3. We did not detect TCE or any other chlorinated VOCs in these samples. PCE exposure occurred among individuals living on the EPA Superfund site, as well as among those living on other plume sites and those living outside any known plumes. Preventive measures should focus on identifying highly exposed groups and reducing their exposures, followed by addressing moderately elevated exposures in the community. Our results demonstrated that PCE in exhaled breath can be used as an effective tool in community engaged environmental health research to evaluate the extent and level of community exposure, increase awareness, and promote residents’ participation in research and site cleanup decision-making.

Remediation of zinc-contaminated groundwater by iron oxide in situ adsorption barriers – From lab to the field

Heavy metals such as zinc cannot be degraded by microorganisms and form long contaminant plumes in groundwater. Conventional methods for remediating heavy metal-contaminated sites are for example excavation and pump-and-treat, which is expensive and requires very long operation times. This induced interest in new technologies such as in situ adsorption barriers for immobilization of heavy metal contamination. In this study, we present steps and criteria from laboratory tests to field studies, which are necessary for a successful implementation of an in situ adsorption barrier for immobilizing zinc. Groundwater and sediment samples from a contaminated site were brought to the lab, where the adsorption of zinc to Goethite nanoparticles was studied in batch and in flow-through systems mimicking field conditions. The Goethite nanoparticles revealed an in situ adsorption capacity of approximately 23 mg Zn per g Goethite. Transport experiments in sediment columns indicated an expected radius of influence of at least 2.8 m for the injection of Goethite nanoparticles. These findings were validated in a pilot-scale field study, where an in situ adsorption barrier of ca. 11 m × 6 m × 4 m was implemented in a zinc-contaminated aquifer. The injected nanoparticles were irreversibly deposited at the desired location within <24 h, and were not dislocated with the groundwater flow. Despite a constantly increasing inflow of zinc to the barrier and the short contact time between Goethite and zinc in the barrier, the dissolved zinc was effectively immobilized for ca. 90 days. Then, the zinc concentrations increased slowly downstream of the barrier, but the barrier still retained most of the zinc from the inflowing groundwater. The study demonstrated the applicability of Goethite nanoparticles to immobilize heavy metals in situ and highlights the criteria for upscaling laboratory-based determinants to field-scale.

Potential of Variovorax paradoxus isolate BFB1_13 for bioremediation of BTEX contaminated sites

Here, we report and discuss the applicability of Variovorax paradoxus strain BFB1_13 in the bioremediation of BTEX contaminated sites. Strain BFB1_13 was capable of degrading all the six BTEX-compounds under both aerobic (O2 conc. 8 mg l−1) and micro-aerobic/oxygen-limited (O2 conc. 0.5 mg l−1) conditions using either individual (8 mg‧l−1) or a mixture of compounds (~ 1.3 mg‧l−1 of each BTEX compound). The BTEX biodegradation capability of SBP-encapsulated cultures (SBP—Small Bioreactor Platform) was also assessed. The fastest degradation rate was observed in the case of aerobic benzene biodegradation (8 mg l−1 per 90 h). Complete biodegradation of other BTEX occurred after at least 168 h of incubation, irrespective of the oxygenation and encapsulation. No statistically significant difference was observed between aerobic and microaerobic BTEX biodegradation. Genes involved in BTEX biodegradation were annotated and degradation pathways were predicted based on whole-genome shotgun sequencing and metabolic analysis. We conclude that V. paradoxus strain BFB1_13 could be used for the development of reactive biobarriers for the containment and in situ decontamination of BTEX contaminated groundwater plumes. Our results suggest that V. paradoxus strain BFB1_13—alone or in co-culture with other BTEX degrading bacterial isolates—can be a new and efficient commercial bioremediation agent for BTEX contaminated sites.

Understanding Contaminant Migration Within a Dynamic River Corridor Through Field Experiments and Reactive Transport Modeling

The behavior of a persistent uranium plume within an extended river corridor at the DOE Hanford site is dominantly controlled by river stage fluctuations in the adjacent Columbia River. The plume behavior is further complicated by substantial heterogeneity in physical and geochemical properties of the host aquifer sediments. Multi-scale field and laboratory experiments and reactive transport modeling were integrated to understand the complex plume behavior influenced by highly variable hydrologic and geochemical conditions in time and space. In this paper, we (1) describe multiple data sets from field-scale uranium adsorption and desorption experiments performed at our experimental well-field, (2) develop a reactive transport model that incorporates hydrologic and geochemical heterogeneities characterized from multi-scale and multi-type datasets and a surface complexation reaction network based on laboratory studies, and (3) compare the modeling and observation results to provide insights on how to refine the conceptual model and reduce prediction uncertainties. The experimental results revealed significant spatial variability in uranium adsorption/desorption behavior, while modeling demonstrated that ambient hydrologic and geochemical conditions and heterogeneities in sediment physical and chemical properties both contributed to complex plume behavior and its persistence. This research underscores the great challenges in adequately characterizing this type of site to model the reactive transport processes over scales of 10 m or more. Our analysis provides important insights into the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by dynamic surface water and groundwater interactions.

The importance of transects for characterizing aged organic contaminant plumes in groundwater

A complex mixture of dissolved organic contaminants, emanating from a many decades-old, residual, dense non-aqueous phase liquid (DNAPL) source, migrates through unconfined, moderately heterogeneous, glacial-derived sediments and sedimentary rock in a residential area of Dane County, Wisconsin, USA. A portion of this contaminant plume intersects a large man-made pond, roughly 400 m downgradient of the source zone. Depth-discrete, multilevel groundwater sampling, detailed sedimentological logs, and hydraulic head profiles were used to delineate the spatial distribution of hydraulic, geologic, organic contaminant, and redox hydrochemical conditions within the established plume along two transects immediately upgradient of the pond. Twenty-one contaminants were detected and classified into four major contaminant groups: chlorinated ethenes, chlorinated ethanes, aromatics (BTEX: benzene, toluene, ethylbenzene, xylene), and aliphatic ketones. Within the glacial sediments and shallow bedrock, zones of reductive dechlorination of chlorinated ethenes and ethanes were juxtaposed with zones of BTEX and ketone degradation. Spatial heterogeneity in the concentration and distribution of contaminant groups and redox conditions was observed over lateral distances of tens of meters and vertical distances of tens of centimeters along the two transects. Although the site was situated in a complex glacial depositional environment, lithologic and hydraulic heterogeneity surprisingly only had a modest influence on the spatial distribution of plume contaminants. Depth-discrete sampling along paired, closely spaced transects (~20 m apart) was essential to assess internal plume composition/concentration evolution along flow paths with strong attenuation over short migration distances. This study shows how paired, highly resolved transects can enhance understanding of transverse and longitudinal variability in areas where contaminant-induced redox conditions control reaction zones and strong plume attenuation.

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOMHC) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOMHC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOMHC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

High‐Resolution Characterization of a Chlorinated Solvent Impacted Aquifer Using a Passive Profiler

AbstractA direct‐drive high‐resolution passive profiler (HRPP) was developed to quantify and delineate concentrations of chlorinated volatile organic compounds (CVOCs), geochemical indicators and CVOC‐degrading microorganisms/genes, as well as to perform compound‐specific stable isotope analysis (CSIA) of CVOCs and estimate interstitial velocity at &lt;30‐cm resolution. The profilers can be coupled together to provide a continuous sample interval and advanced to depths up to approximately 9 m below‐ground surface (bgs) within saturated media where direct‐push techniques are feasible. The HRPP was field tested in a previous dense nonaqueous phase liquid (DNAPL) source zone at the former Naval Air Station in Alameda, CA. HRPP data sets were compared to the following traditional groundwater data sets: CVOC and anion concentrations in standard and multilevel monitoring well water samples, CVOC concentrations in soil core samples, qualitative contaminant profiles delineated with a membrane interface probe (MIP), microbial community and CSIA profiles from Bio‐Traps® deployed in wells, groundwater velocity from passive flux meters (PFMs), lithologic profiles correlated with MIP electrical conductivity (EC), and velocity estimates based on permeability profiles measured with a Geoprobe hydraulic profiling tool (HPT). In some cases, the HRPP data were equivalent to traditional techniques and, in other cases, the HRPP data were more representative of local variability rather than bulk aquifer conditions. Overall the results support the use of the HRPP to provide high‐resolution data on concentrations, velocity, and microbial activity in temporary direct‐push deployments without well installation, providing a new tool to better assess source zones and contaminated groundwater plumes, even in low permeability media, and to increase the fidelity of site transport models.

Evaluating two multi-model simulation–optimization approaches for managing groundwater contaminant plumes

Addressing conceptual model uncertainty using multi-model approaches has become an important topic in groundwater hydrology. Model uncertainty is of practical importance when designing a pump-and-treat system for groundwater remediation, as inappropriate consideration of model uncertainty may ultimately lead to ineffective system designs. This study introduces two multi-model approaches for addressing model uncertainty at a site contaminated by chlorinated hydrocarbons and BTEX compounds. We use a multi-objective simulation–optimization method to design a multiple-well pump-and-treat system to contain contaminant plumes within the site perimeter, while minimizing the pumping rate. The design parameters include the coordinates of the pumping well locations and pumping rates. We consider four groundwater models to address uncertainty in conceptualizing site geology, boundary condition, and recharge. Using two multi-model approaches, we evaluate different design concepts. The first approach is a model selection approach that identifies the critical models, which particularly govern the design process, within the multi-model ensemble. The second approach is a model aggregation approach that identifies system designs that meet the remediation objectives for all models of the ensemble. Results show that the model aggregation approach is a more conservative option, which results in reliable designs at the expense of higher pumping rates. This study evaluates these two approaches within the context of multi-model simulation–optimization, providing insights on multi-model simulation–optimization in groundwater management.