Using Network Analysis and Predictive Functional Analysis to Explore the Fluorotelomer Biotransformation Potential of Soil Microbial Communities.

Microbial transformation of per- and polyfluoroalkyl substances (PFAS), including fluorotelomer-derived PFAS, by native microbial communities in the environment has been widely documented. However, few studies have identified the key microorganisms and their roles during the PFAS biotransformation processes. This study was undertaken to gain more insight into the structure and function of soil microbial communities that are relevant to PFAS biotransformation. We collected 16S rRNA gene sequencing data from 8:2 fluorotelomer alcohol and 6:2 fluorotelomer sulfonate biotransformation studies conducted in soil microcosms under various redox conditions. Through co-occurrence network analysis, several genera, including Variovorax, Rhodococcus, and Cupriavidus, were found to likely play important roles in the biotransformation of fluorotelomers. Additionally, a metagenomic prediction approach (PICRUSt2) identified functional genes, including 6-oxocyclohex-1-ene-carbonyl-CoA hydrolase, cyclohexa-1,5-dienecarbonyl-CoA hydratase, and a fluoride-proton antiporter gene, that may be involved in defluorination. This study pioneers the application of these bioinformatics tools in the analysis of PFAS biotransformation-related sequencing data. Our findings serve as a foundational reference for investigating enzymatic mechanisms of microbial defluorination that may facilitate the development of efficient microbial consortia and/or pure microbial strains for PFAS biotransformation.

On the reliable estimation of sequential Monod kinetic parameters.

While dozens of studies have attempted to estimate the Monod kinetic parameters of microbial reductive dechlorination, published values in the literature vary by 2-6 orders of magnitude. This lack of consensus can be attributed in part to limitations of both experimental design and parameter estimation techniques. To address these issues, Hamiltonian Monte Carlo was used to produce more than one million sets of realistic simulated microcosm data under a variety of experimental conditions. These data were then employed in model fitting experiments using a number of parameter estimation algorithms for determining Monod kinetic parameters. Analysis of data from conventional triplicate microcosms yielded parameter estimates characterized by high collinearity, resulting in poor estimation accuracy and precision. Additionally, confidence intervals computed by commonly used classical regression analysis techniques contained true parameter values much less frequently than their nominal confidence levels. Use of an alternative experimental design, requiring the same number of analyses as conventional experiments but comprised of microcosms with varying initial chlorinated ethene concentrations, is shown to result in order-of-magnitude decreases in parameter uncertainty. A Metropolis algorithm which can be run on a typical personal computer is demonstrated to return more reliable parameter interval estimates.

Biotransformation of 6:2 fluorotelomer sulfonate and microbial community dynamics in water-saturated one-dimensional flow-through columns.

Nearly all per- and polyfluoroalkyl substances (PFAS) biotransformation studies reported to date have been limited to laboratory-scale batch reactors. The fate and transport of PFAS in systems that more closely represent field conditions, i.e., in saturated porous media under flowing conditions, remain largely unexplored. This study investigated the biotransformation of 6:2 fluorotelomer sulfonate (6:2 FTS), a representative PFAS of widespread environmental occurrence, in one-dimensional water-saturated flow-through columns packed with soil obtained from a PFAS-contaminated site. The 305-day column experiments demonstrated that 6:2 FTS biotransformation was rate-limited, where a decrease in pore-water velocity from 3.7 to 2.4 cm/day, resulted in a 21.7-26.1 % decrease in effluent concentrations of 6:2 FTS and higher yields (1.0-1.4 mol% vs. 0.3 mol%) of late-stage biotransformation products (C4C7 perfluoroalkyl carboxylates). Flow interruptions (2 and 7 days) were found to enhance 6:2 FTS biotransformation during the 6-7 pore volumes following flow resumption. Model-fitted 6:2 FTS column biotransformation rates (0.039-0.041 cmw3/gs/d) were ∼3.5 times smaller than those observed in microcosms (0.137 cmw3/gs/d). Additionally, during column experiments, planktonic microbial communities remained relatively stable, whereas the composition of the attached microbial communities shifted along the flow path, which may have been attributed to oxygen availability and the toxicity of 6:2 FTS and associated biotransformation products. Genus Pseudomonas dominated in planktonic microbial communities, while in the attached microbial communities, Rhodococcus decreased and Pelotomaculum increased along the flow path, suggesting their potential involvement in early- and late-stage 6:2 FTS biotransformation, respectively. Overall, this study highlights the importance of incorporating realistic environmental conditions into experimental systems to obtain a more representative assessment of in-situ PFAS biotransformation.

Modeling 1-D aqueous film forming foam transport through the vadose zone under realistic site and release conditions.

Aqueous film forming foams (AFFFs) have been used to extinguish fires since the 1960s, leading to widespread subsurface contamination by per- and polyfluoroalkyl substances (PFAS), an essential component of AFFF. This study presents 1-D simulations of PFAS migration in the vadose zone resulting from AFFF releases. Simulation scenarios used soil profiles from three US Air Force (USAF) installations, encompassing a range of climatic conditions and hydrogeologic environments. A three-component mixture, representative of major constituents of AFFF, facilitated the exploration of competitive and synergistic effects of co-constituents on PFAS migration. To accurately capture unsaturated transport of PFAS in porous media, the model considers (1) surfactant-induced flow, (2) non-linear sorption to the solid phase, (3) competitive accumulation at the air-water interface, and (4) the moisture-dependence of the air-water interfacial area. Defined PFAS releases were consistent with fire training exercises, emergency responses, and accidental spills of record. Simulation results illustrate the importance of hydrogeologic, climatic, geochemical, and AFFF release conditions on PFAS transport and retention. Comparison of field observations and model simulations for Ellsworth AFB indicate that much of the PFOA and PFOS mass is associated with the air-water interface and the solid phase, which limits their migration potential in the vadose zone. Results also show that rates of migration in the aqueous phase are largely controlled by hydrogeologic properties, including recharge rates and hydraulic conductivity. AFFF spill scenarios varying in volume, concentration, and frequency reveal the importance of release characteristics in determining rates of PFAS migration and concentration peaks. Variability is attributed to non-linear sorption processes, where, contrary to simple linear partitioning formulations, transport is strongly affected by the concentration of PFAS species. Simulations also demonstrate the importance of modeling the AFFF as a mixture since competitive interfacial accumulation effects are shown to enhance the mobility of less surface-active PFAS compounds.

Aerobic biotransformation of 6:2 fluorotelomer sulfonate in soils from two aqueous film-forming foam (AFFF)-impacted sites.

Although 6:2 fluorotelomer sulfonate (6:2 FTS) is a common ingredient in aqueous film-forming foam (AFFF) formulations, its environmental fate at AFFF-impacted sites remains poorly understood. This study investigated the biotransformation of 6:2 FTS in microcosms prepared with soils collected from two AFFF-impacted sites; the former Loring Air Force Base (AFB) and Robins AFB. The half-life of 6:2 FTS in Loring soil was 43.3 days; while >60 mol% of initially spiked 6:2 FTS remained in Robins soil microcosms after a 224-day incubation. Differences in initial sulfate concentrations and the depletion of sulfate over the incubation likely contributed to the different 6:2 FTS biotransformation rates between the two soils. At day 224, stable transformation products, i.e., C4C7 perfluoroalkyl carboxylates, were formed with combined molar yields of 13.8 mol% and 1.2 mol% in Loring and Robins soils, respectively. Based on all detected transformation products, the biotransformation pathways of 6:2 FTS in the two soils were proposed. Microbial community analysis suggests that Desulfobacterota microorganisms may promote 6:2 FTS biotransformation via more efficient desulfonation. In addition, species from the genus Sphingomonas, which exhibited higher tolerance to elevated concentrations of 6:2 FTS and its biotransformation products, are likely to have contributed to 6:2 FTS biotransformation. This study demonstrates the potential role of biotransformation processes on the fate of 6:2 FTS at AFFF-impacted sites and highlights the need to characterize site biogeochemical properties for improved assessment of 6:2 FTS biotransformation behavior.

Microbial Reductive Dechlorination by a Commercially Available Dechlorinating Consortium Is Not Inhibited by Perfluoroalkyl Acids (PFAAs) at Field-Relevant Concentrations.

Perfluoroalkyl acids (PFAAs) have been shown to inhibit biodegradation (i.e., organohalide respiration) of chlorinated ethenes. The potential negative impacts of PFAAs on microbial species performing organohalide respiration, particularly Dehalococcoides mccartyi (Dhc), and the efficacy of in situ bioremediation are a critical concern for comingled PFAA-chlorinated ethene plumes. Batch reactor (no soil) and microcosm (with soil) experiments, containing a PFAA mixture and bioaugmented with KB-1, were completed to assess the impact of PFAAs on chlorinated ethene organohalide respiration. In batch reactors, PFAAs delayed complete biodegradation of cis-1,2-dichloroethene (cis-DCE) to ethene. Maximum substrate utilization rates (a metric for quantifying biodegradation rates) were fit to batch reactor experiments using a numerical model that accounted for chlorinated ethene losses to septa. Fitted values for cis-DCE and vinyl chloride biodegradation were significantly lower (p < 0.05) in batch reactors containing ≥50 mg/L PFAAs. Examination of reductive dehalogenase genes implicated in ethene formation revealed a PFAA-associated change in the Dhc community from cells harboring the vcrA gene to those harboring the bvcA gene. Organohalide respiration of chlorinated ethenes was not impaired in microcosm experiments with PFAA concentrations of 38.7 mg/L and less, suggesting that a microbial community containing multiple strains of Dhc is unlikely to be inhibited by PFAAs at lower, environmentally relevant concentrations.

Assessing aerobic biotransformation of 8:2 fluorotelomer alcohol in aqueous film-forming foam (AFFF)-impacted soils: Pathways and microbial community dynamics.

Production of 8:2 fluorotelomer alcohol (8:2 FTOH) for industrial and consumer products, including aqueous film-forming foams (AFFFs) used for firefighting, has resulted in its widespread occurrence in the environment. However, the fate of 8:2 FTOH at AFFF-impacted sites remains largely unknown. Using AFFF-impacted soils from two United States Air Force Bases, microcosm experiments evaluated the aerobic biotransformation of 8:2 FTOH (extent and byproduct formation) and the dose-response on microbial communities due to 8:2 FTOH exposure. Despite different microbial communities, rapid transformation of 8:2 FTOH was observed during a 90-day incubation in the two soils, and 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were detected as major transformation products. Novel transformation products, including perfluoroalkane-like compounds (1H-perfluoroheptane, 1H-perfluorohexane, and perfluoroheptanal) were identified by liquid chromatography-high resolution mass spectrometry (LC-HRMS) and used to develop aerobic 8:2 FTOH biotransformation pathways. Microbial community analysis suggests that species from genus Sphingomonas are potential 8:2 FTOH degraders based on increased abundance in both soils after exposure, and the genus Afipia may be more tolerant to and/or involved in the transformation of 8:2 FTOH at elevated concentrations. These findings demonstrate the potential role of biological processes on PFAS fate at AFFF-impacted sites through fluorotelomer biotransformation.

Biotransformation of 8:2 Fluorotelomer Alcohol in Soil from Aqueous Film-Forming Foams (AFFFs)-Impacted Sites under Nitrate-, Sulfate-, and Iron-Reducing Conditions.

The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) remains largely unknown, especially under the conditions representative of natural subsurface systems. In this study, the biotransformation of 8:2 fluorotelomer alcohol (8:2 FTOH), a component of new-generation AFFF formulations and a byproduct in fluorotelomer-based AFFFs, was investigated under nitrate-, iron-, and sulfate-reducing conditions in microcosms prepared with AFFF-impacted soils. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) and high-resolution mass spectrometry (HRMS) were employed to identify biotransformation products. The biotransformation was much slower under sulfate- and iron-reducing conditions with >60 mol % of initial 8:2 FTOH remaining after ∼400 days compared to a half-life ranging from 12.5 to 36.5 days under nitrate-reducing conditions. Transformation products 8:2 fluorotelomer saturated and unsaturated carboxylic acids (8:2 FTCA and 8:2 FTUA) were detected under all redox conditions, while 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were only observed as transformation products under nitrate-reducing conditions. In addition, 1H-perfluoroheptane (F(CF2)6CF2H) and 3-F-7:3 acid (F(CF2)7CFHCH2COOH) were identified for the first time during 8:2 FTOH biotransformation. Comprehensive biotransformation pathways for 8:2 FTOH are presented, which highlight the importance of accounting for redox condition and the related microbial community in the assessment of PFAS transformations in natural environments.

Influence of Residual Nonaqueous-Phase Liquids (NAPLs) on the Transport and Retention of Perfluoroalkyl Substances.

Per- and polyfluoralkyl substances (PFAS) are known to accumulate at interfaces, and the presence of nonaqueous-phase liquids (NAPLs) could influence the PFAS fate in the subsurface. Experimental and mathematical modeling studies were conducted to investigate the effect of a representative NAPL, tetrachloroethene (PCE), on the transport behavior of PFAS in a quartz sand. Perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA), a 1:1 mixture of PFOS and PFNA, and a mixture of six PFAS (PFOS, PFNA, perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS)) were used to assess PFAS interactions with PCE-NAPL. Batch studies indicated that PFAS partitioning into PCE-NAPL (Knw < 0.1) and adsorption on 60-80 mesh Ottawa sand (Kd < 6 × 10-5 L/g) were minimal. Column studies demonstrated that the presence of residual PCE-NAPL (∼16% saturation) delayed the breakthrough of PFOS and PFNA, with minimal effects on the mobility of PFBS, PFHpA, PFHxS, and PFOA. Breakthrough curves (BTCs) obtained for PFNA and PFOS alone and in mixtures were nearly identical, indicating the absence of competitive adsorption effects. A mathematical model that accounts for NAPL-water interfacial sorption accurately reproduced PFAS BTCs, providing a tool to predict PFAS fate and transport in co-contaminated subsurface environments.

Quantifying Impacts of Microcosm Mass Loss on Kinetic Constant Estimation.

Microcosm experiments to assess microbial reductive dechlorination of chlorinated aliphatic hydrocarbons typically experience 5-50% mass loss due to frequent sampling events and diffusion through septa. A literature review, however, reveals that models fit to such experiments for kinetic constant estimation have generally failed to account for experimental mass loss. To investigate possible resultant bias in best-fit parameters, a series of numerical experiments was conducted in which Monod kinetic models with and without mass loss were fit to more than 1300 synthetic data sets, generated using published microcosm data. Models that failed to account for mass loss resulted in significant fitted parameter bias. Bias ranged from 5 to 45% of the parameter magnitude for Monte Carlo simulations with low (approximately 10%) mass loss to 20-120% for simulations with high (approximately 40%) mass loss. In addition, for high mass loss simulations, best-fit values consistently fell along the bounds of the optimization range. These results suggest that failure to properly account for mass loss in microcosms may lead to inaccurate estimation of kinetic constants and may explain some of the literature-reported variability in these parameters. A model is presented that provides a method for including sampling and diffusional mass losses to improve kinetic constant estimation accuracy.

Influence of aqueous film forming foams on the solubility and mobilization of non-aqueous phase liquid contaminants in quartz sands.

At sites where aqueous film forming foams (AFFFs) are used for fire suppression or training activities, interactions between dissolved foam constituents and organic liquids could alter contaminant migration in the subsurface. In this study, batch reactor and column experiments were conducted to investigate the potential for AFFF solutions to enhance the solubility and mobility of three representative non-aqueous phase liquid (NAPLs), JP-4 jet fuel, trichloroethene (TCE), and tetrachloroethene (PCE). For AFFF concentrations up to 5% wt. (50,000 mg/L), aqueous solubilities of TCE and PCE increased by less than 50%, indicating the absence of micellar solubilization. However, NAPL-water interfacial tensions were reduced to less than 1.5 mN/m and resulted in accumulation of up to 2.25 mg/m2 of AFFF at the NAPL-water interface. To assess the potential for AFFF to mobilize residual (entrapped) NAPL at a field application rate of 3% wt. (30,000 mg/L), columns were packed with two size fractions of Ottawa sands (20-30 mesh and 60-80 mesh) that yielded residual NAPL saturations ranging from 11.7 to 17.6%. Following injection of 3 pore volumes of the 3% wt. AFFF solution, partial mobilization of residual NAPL was observed for PCE, TCE, and JP-4, with saturation reductions of 0.7 to 2% in 20-30 mesh and 0.3% to 1.3% in 60-80 mesh Ottawa sand. The columns were then flushed with an ultralow-IFT surfactant solution consisting of 4% wt. 1:1 Aerosol AY/OT, which resulted in nearly complete mobilization of the remaining residual NAPL. When NAPL desaturation curves were expressed in terms of the total trapping number (NT), the threshold value of NT required for NAPL mobilization by 3% wt. AFFF was approximately 2 × 10-5, consistent with previous studies. These findings demonstrate that AFFF solutions can lead to partial mobilization of residual NAPL, and that the total trapping number concept can be used to predict such behavior a priori. In addition, the observed IFT reductions are sufficient to alter NAPL accumulation and redistribution behavior in the subsurface through enhanced spreading above the water table (e.g., JP-4) or penetration into lower-permeability media (e.g., TCE, PCE).

Exploration of processes governing microbial reductive dechlorination in a heterogeneous aquifer flow cell.

Although microbial reductive dechlorination (MRD) has proven to be an effective approach for in situ treatment of chlorinated ethenes, field implementation of this technology is complicated by many factors, including subsurface heterogeneity, electron donor availability, and distribution of microbial populations. This work presents a coupled experimental and mathematical modeling study designed to explore the influence of heterogeneity on MRD and to assess the suitability of microcosm-derived rate parameters for modeling complex heterogeneous systems. A Monod-based model is applied to simulate a bioremediation experiment conducted in a laboratory-scale aquifer cell packed with aquifer material from the Commerce Street Superfund site in Williston, VT. Results reveal that (uncalibrated) model application of microcosm-derived dechlorination and microbial growth rates for transformation of trichloroethene (TCE), cis-1,2-dichloroethene (cis-DCE), and vinyl chloride (VC) reproduced observed aquifer cell concentration levels and trends. Mean relative errors between predicted and measured effluent concentrations were quantified as 6.7%, 27.0%, 41.5%, 32.0% and 21.6% over time for TCE, cis-DCE, VC, ethene and total volatile fatty acids (fermentable electron donor substrate and carbon source), respectively. The time-averaged extent of MRD (i.e., ethene formation) was well-predicted (4% underprediction), with modeled MRD exhibiting increased deviation from measured values under electron donor limiting conditions (maximum discrepancy of 14%). In contrast, simulations employing a homogeneous (uniform flow) domain resulted in underprediction of MRD extent by an average of 13%, with a maximum discrepancy of 45%. Model sensitivity analysis suggested that trace amounts of natural dissolved organic carbon served as an important fermentable substrate, providing up to 69% of the reducing equivalents consumed for MRD under donor-limiting conditions. Aquifer cell port concentration data and model simulations revealed that ethene formation varied spatially within the domain and was associated with regions of longer residence times. These results demonstrate the strong influence of subsurface heterogeneity on the accuracy of MRD predictions, and highlight the importance of subsurface characterization and the incorporation of flow field uncertainty in model applications for successful design and assessment of in situ bioremediation.

Aqueous Film-Forming Foams Exhibit Greater Interfacial Activity than PFOA, PFOS, or FOSA.

Perfluoroalkyl acids spontaneously concentrate at air-water and non-aqueous phase liquid (NAPL)-water interfaces, which can influence their retention during subsurface transport. This work presents measurements of air- and NAPL-water interfacial tension for synthetic groundwater containing perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorooctanesulfonamide (FOSA), or aqueous film-forming foam (AFFF) formulations at concentrations ranging from 0.1 to greater than 1000 mg/L. The NAPLs tested included dodecane, tetrachloroethylene, and jet fuel. AFFF formulations were less efficient at lowering interfacial tension than PFOA, FPOS, or FOSA substances below 100 mg/L, while above 100 mg/L, these formulations were more effective, achieving tensions of less than 3 mN/m. Infiltration of solutions with such low tension could lead to mobilization of residual NAPL. Equations based on interfacial tension measurements show that concentrations of PFOA, PFOS, and FOSA at the air-water interface were from 2 to 16 times greater than at the NAPL-water interface below 100 mg/L and were 10-50 times greater for AFFF below 20 mg/L. Calculations for unsaturated soil estimate that up to 87% of PFOS mass was at the air-water interface and less than 4% at the dodecane-water interface for bulk-water concentrations below 1 mg/L.

Bioenhanced back diffusion and population dynamics of Dehalococcoides mccartyi strains in heterogeneous porous media.

Diffusion, sorption-desorption, and biodegradation influence chlorinated solvent storage in, and release (mass flux) from, low-permeability media. Although bioenhanced dissolution of non-aqueous phase liquids has been well-documented, less attention has been directed towards biologically-mediated enhanced diffusion from low-permeability media. This process was investigated using a heterogeneous aquifer cell, packed with 20-30 mesh Ottawa sand and lenses of varying permeability (1.0 × 10-12-1.2 × 10-11 m2) and organic carbon (OC) content (<0.1%-2%), underlain by trichloroethene (TCE)-saturated clay. Initial contaminant loading was attained by flushing with 0.5 mM TCE. Total chlorinated ethenes removal by hydraulic flushing was then compared for abiotic and bioaugmented systems (KB-1® SIREM; Guelph, ON). A numerical model incorporating coupled diffusion and (de)sorption facilitated quantification of bio-enhanced TCE release from low-permeability lenses, which ranged from 6% to 53%. Although Dehalococcoides mccartyi (Dhc) 16S rRNA genes were uniformly distributed throughout the porous media, strain-specific distribution, as indicated by the reductive dehalogenase (RDase) genes vcrA, bvcA, and tceA, was influenced by physical and chemical heterogeneity. Cells harboring the bvcA gene comprised 44% of the total RDase genes in the lower clay layer and media surrounding high OC lenses, but only 2% of RDase genes at other locations. Conversely, cells harboring the vcrA gene comprised 50% of RDase genes in low-permeability media compared with 85% at other locations. These results demonstrate the influence of microbial processes on back diffusion, which was most evident in regions with pronounced contrasts in permeability and OC content. Bioenhanced mass transfer and changes in the relative abundance of Dhc strains are likely to impact bioremediation performance in heterogeneous systems.

Development and Validation of a Two-Stage Kinetic Sorption Model for Polymer and Surfactant Transport in Porous Media.

Understanding the sorption processes is critical to the successful design and implementation of a variety of technologies in subsurface application. Most transport models assume minimal interactions between adsorbed species and, thus, are unable to accurately describe the formation of adsorbed bilayers. To address this limitation, a two-stage kinetic sorption model is developed and incorporated into a one-dimensional advective-dispersive-reactive transport simulator. The model is evaluated using data obtained from column experiments conducted with a representative polymer [gum arabic (GA)] and a nonionic surfactant [Witconol 2722 (WT)] under a range of experimental conditions. Model simulations demonstrate that the first-stage polymer/surfactant-surface sorption rate is at least 1 order of magnitude greater than the second-stage rate, associated with bilayer formation, indicating that the first-stage reaction is more favorable. The reversibility of the second-stage sorption process is found to be compound-specific, with irreversible sorption observed for GA and prolonged tailing observed for WT. This study demonstrates that the developed two-stage kinetic model is superior to a two-stage equilibrium-based model in its replication of two-leg breakthrough curves observed in core flood experiments; the normalized root-mean-square error between measurement and regressed model simulations was reduced by an average of 41% with the kinetic approach.

Modeling the influence of coupled mass transfer processes on mass flux downgradient of heterogeneous DNAPL source zones.

Sequestered mass in low permeability zones has been increasingly recognized as an important source of organic chemical contamination that acts to sustain downgradient plume concentrations above regulated levels. However, few modeling studies have investigated the influence of this sequestered mass and associated (coupled) mass transfer processes on plume persistence in complex dense nonaqueous phase liquid (DNAPL) source zones. This paper employs a multiphase flow and transport simulator (a modified version of the modular transport simulator MT3DMS) to explore the two- and three-dimensional evolution of source zone mass distribution and near-source plume persistence for two ensembles of highly heterogeneous DNAPL source zone realizations. Simulations reveal the strong influence of subsurface heterogeneity on the complexity of DNAPL and sequestered (immobile/sorbed) mass distribution. Small zones of entrapped DNAPL are shown to serve as a persistent source of low concentration plumes, difficult to distinguish from other (sorbed and immobile dissolved) sequestered mass sources. Results suggest that the presence of DNAPL tends to control plume longevity in the near-source area; for the examined scenarios, a substantial fraction (43.3-99.2%) of plume life was sustained by DNAPL dissolution processes. The presence of sorptive media and the extent of sorption non-ideality are shown to greatly affect predictions of near-source plume persistence following DNAPL depletion, with plume persistence varying one to two orders of magnitude with the selected sorption model. Results demonstrate the importance of sorption-controlled back diffusion from low permeability zones and reveal the importance of selecting the appropriate sorption model for accurate prediction of plume longevity. Large discrepancies for both DNAPL depletion time and plume longevity were observed between 2-D and 3-D model simulations. Differences between 2- and 3-D predictions increased in the presence of sorption, especially for the case of non-ideal sorption, demonstrating the limitations of employing 2-D predictions for field-scale modeling.

Aqueous Aggregation Behavior of Engineered Superparamagnetic Iron Oxide Nanoparticles: Effects of Oxidative Surface Aging.

For successful aqueous-based applications, it is necessary to fundamentally understand and control nanoparticle dispersivity and stability over a range of dynamic conditions, including variable ionic strengths/types, redox chemistries, and surface ligand reactivity/degradation states (i.e., surface aging). Here, we quantitatively describe the behavior of artificially aged, oleic acid (OA) bilayer coated iron oxide nanoparticles (IONPs) under different scenarios. Hydrogen peroxide (H2O2), used here as a model oxidant under both dark and light ultraviolet (UVA) conditions, was employed to "age" materials, to varying degrees, without increasing ionic strength. Short-term stability experiments indicate that OA-IONPs, while stable in the dark, are effectively destabilized when exposed to UVA/H2O2/•OH based oxidation processes. Compared to bicarbonate, phosphate (1.0 mM) has a net stabilizing effect on OA-IONPs under oxidative conditions, which can be attributed to (surface-based) functional adsorption. Corresponding aggregation kinetics in the presence of monovalent (Na+) and divalent cations (Ca2+) show that attachment efficiencies (α) are strongly dependent on the cation concentrations/types and degree of surface aging. Taken together, our findings directly highlight the need to understand the critical role of particle surface transformation(s), via oxidative aging, among other routes, with regard to the ultimate stability and environmental fate of surface functionalized engineered nanoparticles.

Development and application of a screening model for evaluating bioenhanced dissolution in DNAPL source zones.

In-situ bioremediation, a widely applied treatment technology for source zones contaminated with dense non-aqueous phase liquids (DNAPLs), has proven economical and reasonably efficient for long-term management of contaminated sites. Successful application of this remedial technology, however, requires an understanding of the complex interaction of transport, mass transfer, and biotransformation processes. The bioenhancement factor, which represents the ratio of DNAPL mass transfer under microbially active conditions to that which would occur under abiotic conditions, is commonly used to quantify the effectiveness of a particular bioremediation remedy. To date, little research has been directed towards the development and validation of methods to predict bioenhancement factors under conditions representative of real sites. This work extends an existing, first-order, bioenhancement factor expression to systems with zero-order and Monod kinetics, representative of many source-zone scenarios. The utility of this model for predicting the bioenhancement factor for previously published laboratory and field experiments is evaluated. This evaluation demonstrates the applicability of these simple bioenhancement factors for preliminary experimental design and analysis, and for assessment of dissolution enhancement in ganglia-contaminated source zones. For ease of application, a set of nomographs is presented that graphically depicts the dependence of bioenhancement factor on physicochemical properties. Application of these nomographs is illustrated using data from a well-documented field site. Results suggest that this approach can successfully capture field-scale, as well as column-scale, behavior. Sensitivity analyses reveal that bioenhanced dissolution will critically depend on in-situ biomass concentrations.

In situ measurement and simulation of nano-magnetite mobility in porous media subject to transient salinity.

Nanotechnologies have been proposed for a variety of environmental applications, including subsurface characterization, enhanced oil recovery, and in situ contaminant remediation. For such applications, quantitative predictive models will be of great utility for system design and implementation. Electrolyte chemistry, which can vary substantially within subsurface pore waters, has been shown to strongly influence nanoparticle aggregation and deposition in porous media. Thus, it is essential that mathematical models be capable of tracking changes in electrolyte chemistry and predicting its influence on nanoparticle mobility. In this work, a modified version of a multi-dimensional multispecies transport simulator (SEAWAT) was employed to model nanoparticle transport under transient electrolyte conditions. The modeling effort was supported by experimental measurements of paramagnetic magnetite (Fe3O4) nanoparticle, coated with polyacrylamide-methylpropane sulfonic acid - lauryl acrylate (nMag-PAMPS), mobility in columns packed with 40-50 mesh Ottawa sand. Column effluent analyses and magnetic resonance imaging (MRI) were used to quantify nanoparticle breakthrough and in situ aqueous phase concentrations, respectively. Experimental observations revealed that introduction of de-ionized water into the brine saturated column (80 g L(-1) NaCl + 20 g L(-1) CaCl2) promoted release and remobilization of deposited nanoparticles along a diagonal front, coincident with the variable density flow field. This behavior was accurately captured by the simulation results, which indicated that a two-site deposition-release model provided the best fit to experimental observations, suggesting that heterogeneous nanoparticle-surface interactions governed nanoparticle attachment. These findings illustrate the importance of accounting for both physical and chemical processes associated with changes in electrolyte chemistry when predicting nanoparticle transport behavior in subsurface formations.