Covalently Cross-Linked Polyelectrolyte Complex Nanoparticles with Enhanced Stability against Dissociation at High Ionic Strength.

Polyelectrolyte complex nanoparticles (PECNPs) often fully dissociate into individual polycations (PC) and polyanions (PA) at high salinities. Herein, we introduce a novel type of colloidally stable PECNP in which the PC is cross-linked, in this case branched polyethylenimine (PEI) to limit this dissociation, even in solutions up to 5.2 M NaCl or 5.

Fate and Transformation of 15 Classes of Per- and Polyfluoroalkyl Substances in Aqueous Film-Forming Foam (AFFF)-Amended Soil Microcosms.

The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs), especially those synthesized by electrochemical fluorination (ECF) processes, remains largely unknown. This study evaluated the transformation of AFFF-derived ECF-based precursors in aerobic soil microcosms amended with a historically used AFFF formulation (3M Light Water). Fifteen classes of PFAS, including AFFF components and transformation products, were identified or tentatively identified by suspect screening/nontargeted analysis (SSA/NTA) throughout a 308-day incubation.

Transport and competitive interfacial adsorption of PFOA and PFOS in unsaturated porous media: Experiments and modeling.

Among emerging contaminants, per- and polyfluoroalkyl substances (PFAS) have captured public attention based upon their environmental ubiquity and potential risks to human health. Due to their typical surface release conditions and amphiphilic properties, PFAS tend to sorb to soil and accumulate at the air-water interface within the vadose zone. These processes can result in substantial plume attenuation.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

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.

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.

Modeling coupled nanoparticle aggregation and transport in porous media: a Lagrangian approach.

Changes in nanoparticle size and shape due to particle-particle interactions (i.e., aggregation or agglomeration) may significantly alter particle mobility and retention in porous media.