Mobilization of per- and poly-fluoroalkyl substances (PFAS) in soils with different organic matter contents.

There is considerable interest in addressing soils contaminated with per- and polyfluoroalkyl substances (PFAS) because of the PFAS in the environment and associated health risks. The neutralization of PFAS in situ is challenging. Consequently, mobilizing the PFAS from the contaminated soils into an aqueous solution for subsequent handling has been pursued. Nonetheless, the efficiency of mobilization methods for removing PFAS can vary depending on site-specific factors, including the types and concentrations of PFAS compounds, soil characteristics. In the present study, the removal of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) from artificially contaminated soils was investigated in a 2D laboratory setup using electrokinetic (EK) remediation and hydraulic flushing by applying a hydraulic gradient (HG) for a duration of 15 days. The percent removal of PFOA by EK was consistent (∼80%) after a 15-day treatment for all soils. The removal efficiency of PFOS by EK significantly varied with the OM content, where the PFOS removal increased from 14% at 5% OM to 60% at 50% OM. With HG, the percent removal increased for both PFOA and PFOS from about 20% at 5% OM up to 80% at 75% OM. Based on the results, the mobilization of PFAS from organic soil would be appropriate using both hydraulic flushing and EK considering their applicability and advantages over each other for site-specific factors and requirements.

The use of a fluorine mass balance to demonstrate the mineralization of PFAS by high frequency and high power ultrasound.

High-frequency ultrasound (sonolysis) has been shown as a practical approach for mineralizing PFAS in highly concentrated PFAS waste. However, a fluorine mass balance approach showing complete mineralization for ultrasound treatment has not been elucidated. The impact of ultrasonic power density (W/L) and the presence of co-occurring PFAS on the degradation of individual PFAS are not well understood. In this research, the performance of a 10L sonochemical reactor was assessed for treating synthetic high-concentration PFAS waste with carboxylic and sulfonic perfluoroalkyl surfactants ranging in chain length from four to eight carbons at three different initial concentrations: 6, 55, 183 µM. The mass balance for fluorine was performed using three analytical techniques: triple quadrupole liquid chromatography-mass spectrometry, a fluoride ion selective electrode, and 19F nuclear magnetic resonance. The test results showed near complete mineralization of PFAS in the waste without the formation of intermediate fluorinated by-products. The PFAS mineralization efficiency of the sonolysis treatment at two different power densities for similar initial concentrations were almost identical; the G value at 145 W/L was 9.7*10-3 g/kWh, whereas the G value at 90 W/L was 9.3*10-3 g/kWh. The results of this study highlight the implications for the scalability of the sonolytic process to treat high-concentration PFAS waste.

Contributions of reactor geometry and ultrasound frequency on the efficiency of sonochemical reactor.

An intermediate-scale reactor with 10L capacity and two transducers operating at 700 and 950 kHz frequencies was developed to study the scalability of the sonolytic destruction of Per and Polyfluoroalkyl substance (PFAS). The impact of frequency, height of liquid or power density, and transducer position on reactor performance was evaluated with the potassium iodide (KI) oxidation and calorimetric power. The dual frequency mode of operation has a synergistic effect based on the triiodide concentration, and calorimetric power. The triiodide concentration, and calorimetric power were higher in this mode compared to the combination of both frequencies operating individually. The sonochemical efficiency for an intermediate-scale reactor (10L) was similar that obtained from a bench-scale reactor (2L), showing the scalability of the sonolytic technology. The placement of the transducer at the bottom or side wall of the reactor had no significant impact on the sonochemical reactivity. The superposition of the ultrasonic field from the dual transducer mode (side and bottom) did not produce a synergistic effect compared to the single transducer mode (bottom or side). This can be attributed to a disturbance due to the interaction of ultrasonic fields of two frequencies from each transducer. With the encouraging results scaling up is in progress for site implementation.

A ReaxFF-based molecular dynamics study of the destruction of PFAS due to ultrasound.

This work uses a computational approach to provide a mechanistic explanation for the experimentally observed destruction of per- and polyfluoroalkyl substances (PFAS) in water due to ultrasound. The PFAS compounds have caused a strong public and regulatory response due to their ubiquitous presence in the environment and toxicity to humans. In this research, ReaxFF -based Molecular Dynamics simulation under several temperatures ranging from 373 K to 5,000 K and different environments such as water vapor, O2, N2, and air were performed to understand the mechanism of PFAS destruction. The simulation results showed greater than 98% PFAS degradation was observed within 8 ns under a temperature of 5,000 K in a water vapor phase, replicating the observed micro/nano bubbles implosion and PFAS destruction during the application of ultrasound. Additionally, the manuscript discusses the reaction pathways and how PFAS degradation evolves providing a mechanistic basis for the destruction of PFAS in water due to ultrasound. The simulation showed that small chain molecules C1 and C2 fluoro-radical products are the most dominant species over the simulated period and are the impediment to an efficient degradation of PFAS. Furthermore, this research confirms the empirical findings observations that the mineralization of PFAS molecules occurs without the generation of byproducts. These findings highlight the potential of virtual experiments in complementing laboratory experiments and theoretical projections to enhance the understanding of PFAS mineralization during the application of ultrasound.

Effect of clay content on the mobilization efficiency of per- and polyfluoroalkyl substances (PFAS) from soils by electrokinetics and hydraulic flushing.

The need for the efficient remediation of soils impacted by per- and polyfluoroalkyl substances (PFAS) is substantially growing because of the notable upsurge in societal and regulatory awareness of this class of chemicals. To remediate PFAS-contaminated soils using mobilization approaches, the choice of appropriate techniques highly depends on the soil's composition, particularly the clay content, which significantly affects the soil's permeability. Here, we investigated the PFAS mobilization efficiency from soils with different clay contents by using two techniques: electrokinetic (EK) remediation and hydraulic flushing. Artificial kaolinite was added to a loamy sand soil to prepare four soil blends with clay contents of 5, 25, 50, and 75%, each contaminated with perfluorooctanoic acid (PFOA) and perfulorooctanesulfonic acid (PFOA) at 10,000 µg/kg. EK remediation was conducted by applying a low voltage (30 V) with a current of 100 mA, and hydraulic flushing was carried out by applying a hydraulic gradient (HG) with a slope of 6.7%. Results show that, with a 14-day treatment duration, the EK-mobilization efficiency was enhanced substantially with the increase of clay content (removal of PFOS increased from 20% at 5% clay to 80% at 75% clay), most likely due to the increase of electroosmotic flow due to the higher content of particles having a zeta potential (i.e., clay). For HG, increasing the clay content significantly suppressed the mobilization of PFAS (removal of PFOS decreased from 40% at 5% clay to 10% at 75% clay) due to a notable decrease in the soil's permeability. Based on the results, applying hydraulic flushing and washing techniques for mobilizing PFAS would be appropriate when treating permeable soils with a maximum clay content of about 25%; otherwise, other suitable mobilization techniques such as EKs should be considered.

A Review of PFAS Destruction Technologies.

Per- and polyfluoroalkyl substances (PFASs) are a family of highly toxic emerging contaminants that have caught the attention of both the public and private sectors due to their adverse health impacts on society. The scientific community has been laboriously working on two fronts: (1) adapting already existing and effective technologies in destroying organic contaminants for PFAS remediation and (2) developing new technologies to remediate PFAS. A common characteristic in both areas is the separation/removal of PFASs from other contaminants or media, followed by destruction. The widely adopted separation technologies can remove PFASs from being in contact with humans; however, they remain in the environment and continue to pose health risks. On the other hand, the destructive technologies discussed here can effectively destroy PFAS compounds and fully address society's urgent need to remediate this harmful family of chemical compounds. This review reports and compare widely accepted as well as emerging PFAS destruction technologies. Some of the technologies presented in this review are still under development at the lab scale, while others have already been tested in the field.

Coupled high and low-frequency ultrasound remediation of PFAS-contaminated soils.

Solids such as soils and sediments contaminated with per- and polyfluorinated alkyl substances (PFAS) from exposure to impacted media, e.g., landfill leachate or biosolids, direct contaminated discharge, and contaminant transport from atmospheric deposition, have caused significant environmental pollution. Such solids can act as secondary sources of PFAS for groundwater and surface water contamination. There are currently no proven technologies that can degrade PFAS in soil and sediments in a cost-effective, environmentally-friendly, and energy-efficient manner. This study examines the use of coupled high and low-frequency ultrasound in desorbing and degrading PFAS in soil, thereby achieving concurrent treatment and destruction of PFAS in soil. Two common PFAS, namely perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were used to evaluate treatment performance in soils with both low and high organic matter contents. The test results showed that the ultrasound treatment could significantly reduce PFAS concentrations in artificially contaminated soil; however, no significant degradation was achieved. Ultrasound treatment did improve desorption of PFAS from solid particles, particularly from the highly absorbent organic soil; 68.8 ± 1.8% of PFOA and 45.4 ± 4.1% of PFOS were leached from the soil after ultrasound treatment compared to only 28 ± 0.2% of PFOA and 1 ± 3.1% of PFOSafter desorption in water. This work shows that sonication treatment is an effective technology for the removal of PFAS from solids, however, the presence of solids in the solid-liquid slurry can negatively impact ultrasonic cavitation, inhibiting the sonolytic degradation of desorbed PFAS.

A Review of the Applications, Environmental Release, and Remediation Technologies of Per- and Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFAS) are pollutants that have demonstrated a high level of environmental persistence and are very difficult to remediate. As the body of literature on their environmental effects has increased, so has regulatory and research scrutiny. The widespread usage of PFAS in industrial applications and consumer products, complicated by their environmental release, mobility, fate, and transport, have resulted in multiple exposure routes for humans. Furthermore, low screening levels and stringent regulatory standards that vary by state introduce considerable uncertainty and potential costs in the environmental management of PFAS. The recalcitrant nature of PFAS render their removal difficult, but existing and emerging technologies can be leveraged to destroy or sequester PFAS in a variety of environmental matrices. Additionally, new research on PFAS remediation technologies has emerged to address the efficiency, costs, and other shortcomings of existing remediation methods. Further research on the impact of field parameters such as secondary water quality effects, the presence of co-contaminants and emerging PFAS, reaction mechanisms, defluorination yields, and the decomposition products of treatment technologies is needed to fully evaluate these emerging technologies, and industry attention should focus on treatment train approaches to improve efficiency and reduce the cost of treatment.