A systematic study of the competitive sorption of per- and polyfluoroalkyl substances (PFAS) on colloidal activated carbon.

Treatment of environmental media contaminated with per- and polyfluoroalkyl substances (PFAS) is crucial to mitigate mounting health risks associated with exposure. Colloidal activated carbon (CAC) has shown promise in treating contaminated soils, but understanding the interaction among PFAS during sorption is necessary for optimal remediation. This study investigated the extent to which PFAS of varying chain lengths and functional groups compete for sorption to CAC. Batch tests were conducted with natural soil and spiked water, using CAC at 0.2% w/w to remove seven PFAS with individual starting concentrations up to 0.05 mmol L-1. PFAS sorption to CAC was evaluated in three systems: a composite mixture of all studied compounds, a binary-solute system, and a single-solute system. The sorption experiments exhibited strong PFAS affinity to CAC, with removal rates between 41% and 100%, and solid/liquid partition coefficients (Kd) between 10 and 104 L kg-1. Differences were noticed among the various spiking mixtures, based on perfluorocarbon chain length, functional group, and the starting PFAS concentrations. Competition effects were detected when PFAS were in a multi-solute system, with an average 10% drop in removal, which can evidently become more relevant at higher concentrations, due to the observed non-linearity of the sorption process. The PFAS most vulnerable to competition effects in multi-solute systems were the short-chain perfluoropentanoic acid (PFPeA) and perfluorobutane sulfonic acid (PFBS), with an up to 25% reduction in removal. In bi-solute systems, perfluorooctane sulfonamide (FOSA) dominated over its ionisable counterparts, i.e. perfluorooctane sulfonic acid (PFOS) and perfluorononanoic acid (PFNA), indicating the importance of hydrophobic effects or layer formation in the sorption process. These results underscore the importance of considering competition in PFAS sorption processes when designing and implementing remediation techniques for PFAS-contaminated media.

Per- and polyfluoroalkyl substance (PFAS) retention by colloidal activated carbon (CAC) using dynamic column experiments.

Developing effective remediation methods for per- and polyfluoroalkyl substance (PFAS)-contaminated soils is a substantial step towards counteracting their widespread occurrence and protecting our ecosystems and drinking water sources. Stabilisation of PFAS in the subsurface using colloidal activated carbon (CAC) is an innovative, yet promising technique, requiring better understanding. In this study, dynamic soil column tests were used to assess the retardation of 10 classical perfluoroalkyl acids (PFAAs) (C5-C11 perfluoroalkyl carboxylic acids (PFCAs) and C4, C6, C8 perfluoroalkane sulfonates (PFSAs)) as well as two alternative PFAS (6:2 and 8:2 fluorotelomer sulfonates) using CAC at 0.03% w/w, to investigate the fate and transport of PFAS under CAC treatment applications. Results showed high retardation rates for long-chain PFAS and eight times higher retardation for the CAC-treated soil compared to the non-treated reference soil for the ∑PFAS. Replacement of shorter chain perfluorocarboxylic acids (PFCAs), such as perfluoropentanoic acid (PFPeA), by longer chained PFAS was observed, indicating competition effects. Partitioning coefficients (Kd values) were calculated for the CAC fraction at ∼103-105 L kg-1 for individual PFAS, while there was a significant positive correlation (p < 0.05) between perfluorocarbon chain length and Kd. Mass balance calculations showed 37% retention of ∑PFAS in treated soil columns after completion of the experiments and 99.7% higher retention rates than the reference soil. Redistribution and elution of CAC were noticed and quantified through organic carbon analysis, which showed a 23% loss of carbon during the experiments. These findings are a step towards better understanding the extent of CAC's potential for remediation of PFAS-contaminated soil and groundwater and the limitations of its applications.

Electrokinetic remediation for removal of per- and polyfluoroalkyl substances (PFASs) from contaminated soil.

Uncontrolled use and disposal of per- and polyfluoroalkyl substances (PFASs) in recent decades has resulted in extensive soil and groundwater contamination, necessitating counteraction. Electrokinetic remediation (EKR) offers a promising approach to in-situ soil remediation. Two novel modifications to conventional EKR were tested for the first time in a laboratory-scale study, to explore the capacity of EKR for PFAS removal. The first modification was a two-compartment setup designed for PFAS extraction from soil to an electrolyte-filled chamber. The second was a single-compartment setup designed to transport and confine contaminants in a chamber filled with granular activated carbon (GAC), thus, combining extraction with stabilisation. Electromigration varied for individual compounds, based mainly on perfluorocarbon chain length and functional group. The results indicated up to 89% concentration and extraction of ∑PFASs for the two-compartment setup, with removal efficiency reaching 99% for individual PFASs with C ≤ 6. Removed PFASs were concentrated adjacent to the anode at the anion exchange membrane, while short-chain compounds were extracted in the anolyte. The single-compartment setup achieved 75% extraction and accumulation of ∑PFASs in GAC. This demonstrates, for the first time, good effectiveness of coupling EKR with AC stabilisation for PFAS removal from soil. Perfluorocarbon chain length was a dominant factor affecting treatment efficiency in both setups, with very high removal rates for short-chain PFASs.

Electrodialytic per- and polyfluoroalkyl substances (PFASs) removal mechanism for contaminated soil.

Contamination of soils with per- and polyfluoroalkyl substances (PFASs) is a global problem, in particular at fire-fighter training sites due to the usage of PFAS-containing aqueous fire-fighting foams (AFFFs). In this study, an electrodialytic remediation method was applied for the first time to remove PFASs from contaminated soil. The electrodialytic remediation system was evaluated in a laboratory-scale experiment with current densities of 0.19 mA cm-2 and 0.38 mA cm-2 over 21 days, using PFAS-contaminated soil from a fire-fighter training site at Stockholm Arlanda Airport, Sweden. Of the 23 PFASs targeted, significant (p < 0.05) PFAS electromigration towards the anode was observed for C3-C7 perfluoroalkyl carboxylates (PFCAs) (PFBA, PFPeA, PFHxA, PFOA) and C4, C6, and C8 perfluoroalkane sulfonates (PFSAs) (PFBS, PFHxS, PFOS) since these PFASs were predominantly negatively charged. In contrast to the electromigration of the charged PFASs, N-methyl perfluorooctane sulfonamide (MeFOSA), perfluorooctane sulfonamidoacetic acid (FOSAA) and ethyl FOSAA (EtFOSAA) showed significant (p < 0.05) transport towards the cathode, which is probably attributed to electro-osmotic flow of these predominantly neutral PFASs. Mass balance calculations showed that for the shortest-chained PFASs (i.e., PFBA, PFPeA, PFHxA, PFBS, and PFHxS), up to 20% was extracted from the soil to the anolyte, which showed that electrodialysis is a possible in-situ remediation technique for PFAS-contaminated soil.

Fabrication and Characterization of Flexible and Miniaturized Humidity Sensors Using Screen-Printed TiO2 Nanoparticles as Sensitive Layer.

This paper describes the fabrication and the characterization of an original example of a miniaturized resistive-type humidity sensor, printed on flexible substrate in a large-scale manner. The fabrication process involves laser ablation for the design of interdigitated electrodes on PET (Poly-Ethylene Terephthalate) substrate and a screen-printing process for the deposition of the sensitive material, which is based on TiO2 nanoparticles. The laser ablation process was carefully optimized to obtain micro-scale and well-resolved electrodes on PET substrate. A functional paste based on cellulose was prepared in order to allow the precise screen-printing of the TiO2 nanoparticles as sensing material on the top of the electrodes. The current against voltage (I-V) characteristic of the sensor showed good linearity and potential for low-power operation. The results of a humidity-sensing investigation and mechanical testing showed that the fabricated miniaturized sensors have excellent mechanical stability, sensing characteristics, good repeatability, and relatively fast response/recovery times operating at room temperature.

Humidity Sensing Properties of Paper Substrates and Their Passivation with ZnO Nanoparticles for Sensor Applications.

In this paper, we investigated the effect of humidity on paper substrates and propose a simple and low-cost method for their passivation using ZnO nanoparticles. To this end, we built paper-based microdevices based on an interdigitated electrode (IDE) configuration by means of a mask-less laser patterning method on simple commercial printing papers. Initial resistive measurements indicate that a paper substrate with a porous surface can be used as a cost-effective, sensitive and disposable humidity sensor in the 20% to 70% relative humidity (RH) range. Successive spin-coated layers of ZnO nanoparticles then, control the effect of humidity. Using this approach, the sensors become passive to relative humidity changes, paving the way to the development of ZnO-based gas sensors on paper substrates insensitive to humidity.