The chemical properties of perfluoroalkyl and polyfluoroalkyl substances (PFAS) pose a significant remediation challenge. This study investigated smoldering combustion to destroy PFAS while scaling up from the lab to field implementation. The first phase consisted of bench-scale tests using a model soil system. Calcium oxide (CaO) was used as a soil amendment in some of the test cases. For all test conditions, greater than 99.9% removal of PFAS was achieved. Post-treatment soils without CaO amendments were found to have a significant reduction in total fluorine concentrations, while the fluorine concentrations in soils with CaO amendments were similar following treatment. This suggests that fluorine emissions from smoldering treatment of PFAS are captured by the presence of the calcium ion (Ca2+). Using new analytical methods, we better characterized the mass balance of the system. These lab results were carried out in a pilot study using soils from a PFAS-impacted site. Two large-scale tests treating 10 m3 of soil were completed. Results of the large-scale smoldering tests agreed with the results from the lab phase. The results from both phases provide a greater understanding of the fate of PFAS when it is treated by smoldering and detail the first large-scale demonstration of smoldering treatment for PFAS-impacted soils.

Per- and polyfluoroalkyl substances (PFAS) encompass over 9000 chemicals utilized in various industrial and commercial applications. However, the quantification of PFAS using standard commercial analytical methods is currently limited to <50 selected compounds. To address this issue, the total oxidizable precursor (TOP) assay was developed, allowing for the oxidative conversion of previously undetectable PFAS precursors into measurable PFAS. This study investigated different sample processing methods to address post-oxidation PFAS loss identified in literature. Using PFOS as a probe molecule, up to 50 % loss of PFOS was identified during sample work-up. It was determined that the use of mass-labelled PFOS and methanolic acetic acid to chemically quench the sample post-oxidation improved PFOS recovery and allowed for correction of any remaining PFOS loss. The use of ultraviolet (UV) light was then investigated as an activator in contrast to the standard thermal activation method. A comparative evaluation was conducted to assess the recovery and conversion of perfluorooctanoic acid (PFOA), PFOS, and 6:2 fluorotelomer sulfonate (6:2 FTS) using both the heat-activated and UV-activated TOP assays. Results demonstrated that the UV-activated TOP assay achieved complete (100 %) oxidation of 6:2 FTS within 7.5 min, resulting in a total yield of generated perfluorinated carboxylic acids (PFCAs) at 108 ± 8 %. The study concluded by investigating the UV-activated TOP assay for its application on various aqueous film forming foam (AFFF) formulations and two AFFF samples drained from military aircraft rescue firefighting vehicles (ARFFVs). Analysis of these AFFF samples were supported by high resolution mass spectrometry and an expanded analytical suite, identifying several fluorotelomer precursors. The findings of this study provide compelling evidence that modifications in sample processing, work-up procedures, expansion of initial PFAS calibration standards, and UV-activation methods enhance the TOP assay, positioning it as a more reliable and quantitative analytical tool for PFAS characterization.

As perand polyfluoroalkyl substances (PFAS) infiltrate the environment via industrial, commercial, and domestic sources, the demand for robust, cost-effective, and straightforward analytical assays intensifies to enhance PFAS characterization and quantification. To address this demand, this study introduces a novel UV-H 2 O 2 -TOP assay, identifying optimal parameters such as pH (5 -9), oxidant concentration (500 mM H 2 O 2 ), activation rate (63 mM H 2 O 2 h -1 ), and an acceptable total organic carbon (TOC) limit (-1000 mg/L TOC) to achieve maximum PFAA precursor conversion. Additional work was performed further optimizing the UV -TOP assay, by confirming its superiority to heat activation, identifying the effectiveness of different persulfate salts, and investigating different concentrations of sodium persulfate and sodium hydroxide at a 1:2.5 ratio on PFCA yield. Our investigation concluded by applying the UV-H 2 O 2 -TOP assay, using sodium persulfate as the TOP assay oxidant, to 6:2 FTS and five different AFFF samples. High -resolution mass spectrometry and an expanded analytical suite support sample analysis, facilitating direct quantification of ultra -short chain perfluoroalkyl carboxylates (PFCAs) and common fluorotelomer compounds including 5:3/5:1:2 fluorotelomer betaine and 6:2 fluorotelomer sulfonamido betaine. Results highlight several advantages of this tandem UV -activated method, including enhanced preservation of perfluoroalkyl chains (post -oxidation of 6:2 fluorotelomer sulfonate resulted in 28 % PFHpA, 47 % PFHxA, 25 % C3 -C5 PFCA), capacity to handle high TOC limits (1000 mg/L TOC), and ability to incorporate higher persulfate concentrations in a single oxidation cycle.

Horizontal ball mills (HBMs) have been proven capable of remediating per- and polyfluoroalkyl substances (PFAS) in soil. Industrial-sized HBMs, which could easily be transported to impacted locations for on-site, ex-situ remediation, are readily available. This study examined PFAS degradation using an industrial-scale, 267 L cylinder HBM. This is the typical scale used in the industry before field application. Near-complete destruction of 6:2 fluorotelomer sulfonate (6:2 FTS), as well as the non-target PFAS in a modern fluorotelomer-based aqueous film forming foam (AFFF), was achieved when spiked onto nepheline syenite sand (NSS) and using potassium hydroxide (KOH) as a co-milling reagent. Perfluorooctanesulfonate (PFOS) showed much better and more consistent results with scale-up regardless of KOH. Perfluorooctanoate (PFOA) was examined for the first time using a HBM and behaved similarly to PFOS. Highly challenging field soils from a former firefighting training area (FFTA) were purposefully used to test the limits of the HBM. To quantify the effectiveness, free fluoride analysis was used; changes between unmilled and milled soil were measured up to 7.8 mg/kg, which is the equivalent of 12 mg/kg PFOS. Notably, this does not factor in insoluble fluoride complexes that may form in milled soils, so the actual amount of PFAS destroyed may be higher. Soil health, evaluated through the assessment of key microbial and associated plant health parameters, was not significantly affected as a result of milling, although it was characterized as poor to begin with. Leachability reached 100 % in milled soil with KOH, but already ranged from 81 to 96 % in unmilled soil. A limited assessment of the hazards associated with the inhalation of PFAS-impacted dust from ball-milling, as well as the cross-contamination potential to the environment, showed that the risk was low in both cases; however, precautions should always be taken.

The effect of applied stress (20, 60, and 150 kPa) on the diffusion of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) through a geosynthetic clay liner (GCL) is examined. The diffusion coefficients deduced from GCL diffusion tests for PFOA and PFOS decrease linearly with decreasing final bulk GCL void ratio (increasing applied stresses). The different components of the same GCL are also tested for PFOA and PFOS sorption. No statistically significant sorption of PFOA is observed for any of the components of the GCL. However, some sorption of PFOS onto the cover and carrier geotextiles of the GCL is observed with in an average distribution coefficient, K-d similar to 2.22 ml/g for the GCL. Permeants containing different PFAS compounds are tested to assess their impact on the Geomembrane (GMB) - GCL interface transmissivity in composite liners. Results show PFAS concentrations up to 20 ppm had negligible impact on the GMB-GCL interface transmissivity. Lastly, the GCL specimens extracted from the diffusion tests are tested for hydraulic conductivity. No impact of PFAS is seen on the hydraulic conductivity of GCLs subjected to high applied loads, but a small increase is seen on the GCLs subjected to relatively low applied stresses.

We studied the occurrence of dissolved thiolated Arsenic (As) in legacy tailings systems in Ontario and Nova Scotia, Canada, and used aqueous and mineralogical speciation analyses to assess its governing geochemical controls. Surface-accessible and inundated tailings in Cobalt, Ontario, contained ∼1 wt-% As mainly hosted in secondary arsenate minerals (erythrite, yukonite, and others) and traces of primary sulfide minerals (cobaltite, gersdorffite and others). Significant fractions of thiolated As (up to 5.9 % of total dissolved As) were detected in aqueous porewater and surface water samples from these sites, comprising mostly monothioarsenate, and smaller amounts of di- and tri-thioarsenates as well as methylated thioarsenates. Tailings at the Goldenville and Montague sites in Nova Scotia contained less (<0.5 wt-%) As, hosted mostly in arsenopyrite and As-bearing pyrite, than the Cobalt sites, but exhibited higher proportions of dissolved thiolated As (up to 17.3 % of total dissolved As, mostly mono- and di-thioarsenate and traces of tri-thioarsenate). Dissolved thiolated As was most abundant in sub-oxic porewaters and inundated tailings samples across the studied sites, and its concentrations were strongly related to the prevailing redox conditions and porewater hydrochemistry, and to a lesser extent, the As-bearing mineralogy. Our novel results demonstrate that thiolated As species play an important role in the cycling of As in mine waste systems and surrounding environments, and should be considered in mine waste management strategies for high-As sites.

&lt;p&gt;Per- and polyfluoroalkyl substances (PFAS) are a diverse group of manmade, fluorinated organic chemicals that gained notoriety for their diverse application, widespread distribution in the environment and toxicity. One of the main sources of PFAS to the environment is through aqueous film forming foam (AFFF), intended for use on fuel fires. AFFF may enter the environment through system testing, training activities, emergency use or accidental release. When AFFF enters the environment PFAS readily adsorb to porous media through hydrophobic and electrostatic interactions. As a result, PFAS impacted porous media may act as a long-term source of contamination to groundwater, potentially influencing water resources and human health. There is a demand for effective treatment of PFAS impacted porous media. Ball milling has emerged as a potential treatment option for PFAS, however, the viability of treating AFFF impacted porous media has been seldom explored. In this work four AFFF formulations were amended onto silica sand and milled without and with the use of potassium hydroxide (KOH) as a co-milling reagent. Six hour milling trials were conducted using a planetary ball mill with stainless steel grinding media. Significant destruction of perfluorosulfonic acids, perfluorocarboxylic acids (PFCAs), fluorotelomer sulfonates, fluorotelomer betaines and fluorotelomer sulfonamido betaines was observed. With the use of KOH as a co-milling reagent the total PFAS destruction percentage in all four AFFFs exceeded 90%. Greater destruction of PFAS was observed in fluorotelomer dominant AFFFs when compared to perfluoroalkyl acid dominant AFFFs. PFCAs and soluble fluoride were identified as destruction byproducts. KOH as a co-milling reagent had the effect of reducing PFCA byproduct formation and increasing fluoride recovery in three of four AFFFs. Fluoride recoveries indicate PFAS molecule defluorination occurs by ball milling. When PFAS in AFFF is compared to PFAS destruction in single analyte trials, less destruction is observed, displaying the necessity of evaluating realistic AFFF contamination events over single or multi analyte mixtures.&lt;/p&gt;

Metal nanomaterials, such as silver and copper, are often incorporated into commercial textiles to take advantage of their Antibacterial and antiviral properties. The goal of this study was to identify the most parsimonious method for the synthesis of silver, copper, or silver/copper bimetallic treated textiles. To accomplish this eight different methods were employed to synthesize silver, copper, and silver/copper functionalized cotton batting textiles. Using silver and copper nitrate as precursors, different reagents were used to initiate/catalyze the deposition of metal, including: (1) no additive, (2) sodium bicarbonate, (3) green tea, (4) sodium hydroxide, (5) ammonia, (6, 7) sodium hydroxide/ammonia at a 1:2 and 1:4 ratio, and (8) sodium borohydride. The use of sodium bicarbonate as a reagent to reduce silver onto cotton has not been used previously in literature and was compared to established methods. All synthesis methods were performed at 80 °C for one hour following textile addition to the solutions. The products were characterized by x-ray fluorescence (XRF) analysis for quantitative determination of the metal content and x-ray absorption near edge structure (XANES) analysis for silver and copper speciation on the textile. Scanning electron microscopy (SEM) with energy dispersive x-ray (EDX) and size distribution inductively coupled plasma mass spectrometry (ICP-MS) were used to further characterize the products of the sodium bicarbonate, sodium hydroxide, and sodium borohydride synthesis methods following ashing of the textile. For the silver treatment methods (1 mM Ag +), sodium bicarbonate and sodium hydroxide resulted in the highest amounts of silver on the textile (8900 mg Ag/kg textile and 7600 mg Ag/kg textile) and for copper treatment (1 mM Cu +) the sodium hydroxide and sodium hydroxide/ammonium hydroxide resulted in the highest amounts of copper on the textile (3800 mg Ag/kg textile and 2500 mg Ag/kg textile). Formation of copper oxide was dependent on the pH of the solution, with 4 mM ammonia and other high pH solutions resulting in majority of the copper on the textile existing as copper oxide, with smaller amounts of ionic-bound copper. The identified parsimonious methods will lend themselves to the efficient manufacturing of antibacterial and antiviral textiles, or the development of multifunctionalized smart textiles.

Understanding how per- and poly-fluoroalkyl substances (PFAS) are transported is critical to site characterization, monitoring, risk assessment, and remediation planning. This includes an understanding of PFAS retention and release at air-water interfaces. These interfaces exist throughout the vadose zone, but can also exist as trapped air bubbles created by water table fluctuations, recharge, and biogenic gas production. In addition to being directly applicable to transport through trapped gas zones at PFAS-impacted sites, laboratory experiments using emplaced trapped gas (quasi-saturated conditions) provide a controlled method to investigate PFAS behavior, including the effects of different PFAS, concentrations, and mixtures. In this study, a series of laboratory experiments was conducted using one-dimensional sand-packed columns (20 cm × 7 cm dia.). Trapped air was emplaced by sequential drainage and imbibition to create quasi-saturated conditions. Each experiment included separate injections of non-reactive tracer (NaCl) and PFAS solutions through both water-saturated and quasi-saturated columns. A clean, low organic carbon sand was used to eliminate solid-phase sorption (verified through comparison of non-reactive tracer and PFAS breakthrough in the water-saturated columns) and to isolate the effect of air-water interfaces. Experiments were conducted using single-component solutions of PFOA, PFOS and 6:2 FTS, as well as mixtures of those PFAS, at concentrations of 0.1-1 mg/L. Experiments were also conducted using diluted aqueous film-forming foam (AFFF) solutions. Measured retardation factors in triplicate experiments were used to estimate air-water partitioning coefficients.The results showed that PFAS breakthrough was significantly delayed in the presence of trapped air bubbles. Breakthrough delay was greater for PFOS than for PFOA or 6:2 FTS, and was greater for lower PFAS concentrations, for the range of concentrations used in these experiments. For PFAS mixtures, differences in retention were sufficient to completely separate breakthrough (i.e., PFOA and 6:2 FTS achieved complete breakthrough prior to any PFOS arrival) even over short (20 cm) distances. However, the behavior of each PFAS tested was altered by the presence of other PFAS, with PFOA and 6:2 FTS experiencing earlier breakthrough at higher concentrations (concentration overshoot) in the presence of PFOS. Mixture effects were also observed for branched and linear PFOS isomers, and for AFFF solutions, which was further complicated by the presence of hydrocarbon surfactants. The experimental results will be presented along with numerical simulations of PFAS transport subject to air-water partitioning, both to interpret the behavior of PFAS mixtures in experimental systems and to explore the implications of mixture transport in more complex field scenarios.

As the global issue of PFAS contamination in water continues to grow there exists a need for technologies capable of fully mineralizing PFAS in water, with destruction being measured as both a loss of the initial PFAS and a quantitative recovery of the resultant fluoride ions. This study investigates the use of sulfite and iodide in a bicarbonate-buffered alkaline system activated with ultraviolet (UV) light to destroy PFAS. The UV/sulfite/iodide system creates a reductive environment through the generation of aqueous electrons, which can degrade PFAS. The extent of degradation and defluorination was explored for perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), 6:2 fluorotelomer sulfonic acid (6:2 FTS), and perfluorobutane sulfonic acid (PFBS). An initial UV/sulfite/iodide system achieved 100 % degradation and > 90 % defluorination for PFOS, PFOA, and 6:2 FTS, but was not capable of completely degrading PFBS. Transformation product elucidation experiments were performed for PFOS under different UV systems, and 6:2 FtSaB using the initial UV/sulfite/iodide system. Several transformation products were identified including -nF/+nH PFOS (n = 1-13), -F/+H shorter-chain PFSAs, 6:2 fluorotelomer sulfonamidoamine (6:2 FtSaAm), 6:2 fluorotelomer sulfonamide, and 6:2 fluorotelomer unsaturated sulfonamide. Novel identification of -F/ +H perfluoropropane sulfonic acid (PFPS) and -F/+H perfluoroethane sulfonic acid (PFES) following degradation of PFOS confirms C\\C bond cleavage, and different isomers of -F/+H PFOS confirms the potential for C\\F bond cleavage to occur throughout the perfluoroalkyl chain. Additional optimization experiments were performed aiming to fully degrade PFBS. The optimal protocol found in this study involved an elevated initial sulfite concentration and adding additional sulfite at regular intervals during UV-activation, achieving >99.9 % destruction and complete quantitative defluorination of PFBS.

Ball milling has emerged as a promising destructive technique for treating per- and polyfluoroalkyl substances (PFAS)-impacted soils. Environmental media properties such as reactive species generated upon ball milling and particle size are postulated to influence the effectiveness of the technology. In this study, four media types amended with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were planetary ball milled to investigate destruction, fluoride recovery without additional co-milling reagents and the relationship between PFOA and PFOS destruction, particle size during milling, and electron generation. Silica sand, nepheline syenite sand, calcite and marble were sieved to achieve similar initial particle sizes (6/35 distribution), amended with PFOA and PFOS, and milled for 4 h. Particle size analysis was conducted throughout milling and 2,2-diphenyl-1-picrylhydrazyl (DPPH•) was used as a radical scavenger to assess electron generation from the four media types. Particle size reduction was observed to be positively correlated to PFOA and PFOS destruction and DPPH• neutralization (demonstrating electron generation by milling) in silica sand and nepheline syenite sand. Milling of a fine fraction (< 500 μm) of silica sand revealed less destruction compared to the 6/35 distribution suggesting the ability to fracture grains in silicate media is integral to PFOA and PFOS destruction. DPPH• neutralization was demonstrated in all four amended media types, confirming silicate sands and calcium carbonates generate electrons as a reactive species during ball milling. Fluoride loss as a function of milling time was observed in all amended media types. A sodium fluoride (NaF) spiked was used to quantify fluoride loss in the media independent of PFAS. A method was developed using the NaF-amended media fluoride concentrations to estimate the total fluorine liberated from PFOA and PFOS by ball milling. Estimates produced suggest complete recovery of theoretical fluorine yield is obtained. Data from this study was used to propose a reductive destruction mechanism for PFOA and PFOS.

Silver nanomaterials (Ag NMs) have been used in a variety of commercial products to take advantage of their antimicrobial properties. However, there are concerns that these AgNMs can be released during/after use and enter wastewater streams, potentially impacting aquatic systems or accumulating in wastewater biosolids. Biosolids, which are a residual of wastewater treatment processes, have been found to contain AgNMs and are frequently used as agricultural fertilizer. Since the function of soil microbial communities is imperative to nutrient cycling and agricultural productivity, it is important to characterize and assess the effects that silver nanomaterials could have in agricultural soils. In this study agricultural soil was amended with pristine engineered (PVP-coated or uncoated AgNMs), aged silver (sulphidized or released from textiles) nanomaterials, and ionic silver to determine the fate and toxicity over the course of three months. Exposures were carried out at various environmentally relevant concentrations (1 and 10 mg Ag/kg soil) representing between 30 to over 800 years of equivalent biosolid loadings. Over thirteen different methodologies and measures were used throughout this study to assess for potential effects of the silver nanomaterials on soil, including microbial community composition, average well colour development (AWCD) and enzymatic activity. Overall, the AgNM exposures did not exhibit significant toxic effects to the soil microbial communities in terms of density, activity, function and diversity. However, the positive ionic silver treatment (100 mg Ag/kg soil) resulted in suppression to microbial activity while also resulting in significantly higher populations of Frankia alni (nitrogen-fixer) and Arenimonas malthae (phytopathogen) as compared to the negative control (p < 0.05, Tukey HSD) which warrants further investigation.

The transport of per-and polyfluoroalkyl substances (PFAS) in soil and groundwater is important for site investigation, risk characterization, and remediation planning. The adsorption of PFAS at air-water interfaces has been shown to significantly contribute to PFAS retention, with subsequent effects on concentrations and the time scales of transport. In this study, column experiments were conducted to investigate the transport of perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and 6:2 fluorotelomer sulfonate (6:2 FTS) individually and in binary mixtures in the presence of a trapped gas phase, using clean sands to isolate adsorption to air-water interfaces. Consistent with previous studies, the transport of PFOS, PFOA, and 6:2 FTS was retarded by adsorption at the air-water interface, with greater retention of PFOS due to its higher affinity for the air-water interface. Chromatographic separation occurred in the experiments using binary mixtures of PFOS and PFOA, with greater retention at lower influent concentrations. The mixture experiments also showed enhanced breakthrough of PFOA in the presence of PFOS, where effluent concentrations of PFOA were temporarily greater than the influent concentration prior to the breakthrough of PFOS. This enhanced breakthrough was attributed to competition between PFOS and PFOA for adsorption to the air-water interface.

There is a need for destructive technologies for per- and polyfluoroalkyl substances (PFAS) in soil. While planetary ball mill have been shown successful degradation of PFAS, there are issues surrounding scale up (maximum size is typically 0.5 L cylinders). While having lower energy outputs, horizontal ball mills, for which scale up is not a limiting factor, already exist at commercial/industrial sizes from the mining, metallurgic and agricultural industries, which could be re-purposed. This study evaluated the effectiveness of horizontal ball mills in degrading perfluorooctanesulfonate (PFOS), 6:2 fluorotelomer sulfonate (6:2 FTSA), and aqueous film forming foam (AFFF) spiked on nepheline syenite sand. Horizontal ball milling was also applied to two different soil types (sand dominant and clay dominant) collected from a firefighting training area (FFTA). Liquid chromatography tandem mass spectrometry was used to track 21 target PFAS throughout the milling process. High-resolution accurate mass spectrometry was also used to identify the presence and degradation of 19 non-target fluorotelomer substances, including 6:2 fluorotelomer sulfonamido betaine (FtSaB), 7:3 fluorotelomer betaine (FtB), and 6:2 fluorotelomer thioether amido sulfonate (FtTAoS). In the presence of potassium hydroxide (KOH), used as a co-milling reagent, PFOS, 6:2 FTSA, and the non-target fluorotelomer substances in the AFFF were found to undergo upwards of 81%, 97%, and 100% degradation, respectively. Despite the inherent added complexity associated with field soils, better PFAS degradation was observed on the FFTA soils over the spiked NSS, and more specifically, on the FFTA clay over the FFTA sand. These results held through scale-up, going from the 1 L to the 25 L cylinders. The results of this study support further scale-up in preparation for on-site pilot tests.

Per- and polyfluoroalkyl substances (PFAS) are a challenging class of environmental pollutants due to a lack available destructive remediation technologies. Understanding the fundamental mechanisms for degradation of PFAS is key for the development of field scalable and in-situ destructive based remediation technologies. This study aimed to elucidate and refine the current understanding of PFAS degradation mechanisms in water through a series of controlled gamma irradiation studies. Gamma irradiation of PFAS was performed using a cobalt-60 source in a batch irradiation up to 80 kGy at the Australian Nuclear Science and Technology Organization. Perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), 6:2 fluorotelomer sulfonate (6:2 FTS), and a suite of thirteen different PFAS (including C4-C12 PFCAs, C4, C6, C8 PFSAs, and PFOSA) were irradiated to investigate degradation, influence of pH, chain length, and transformation. High resolution mass spectrometry was used to identify more than 80 fluorinated transformation products throughout the degradation experiments. These included the -F/+H, -F/+OH, -F/CH 2 OH exchanged PFAS and n-1 PFCA, amongst others. Given the reactive species present (hydroxyl radicals ( · OH), hydrogen radicals ( · H) and aqueous electrons (e - aq )), and the degradation products formed it was shown that aqueous electrons were the key reactive species responsible for initial PFAS degradation. Most importantly, based on degradation product formation, we found that the initial -F/+H does not have to occur at the α-fluoride (nearest the functional head group), rather occuring throughout the chain length leading to more complex degradation pathways than previously postulated. While our results support some of the reaction steps postulated in the literature, we have developed a unified 16 step and 3 pathway schematic of degradation supported by experimental observations.

Per- and polyfluoroalkyl substances (PFAS) are a challenging class of environmental pollutants due to a lack of available destructive remediation technologies. Understanding the fundamental mechanisms for degradation of PFAS is key for the development of field scalable and in-situ destructive based remediation technologies. This study aimed to elucidate and refine the current understanding of PFAS degradation mechanisms in water through a series of controlled gamma irradiation studies. Gamma irradiation of PFAS was performed using a cobalt-60 source in a batch irradiation up to 80 kGy at the Australian Nuclear Science and Technology Organisation. Perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), 6:2 fluorotelomer sulfonate (6:2 FTS), and a suite of thirteen different PFAS (including C4-C12 PFCAs, C4, C6, C8 PFSAs, and FOSA) were irradiated to investigate degradation, influence of pH, chain length, and transformation. High resolution mass spectrometry was used to identify more than 80 fluorinated transformation products throughout the degradation experiments. These included the -F/+H, -F/+OH, -F/CH2OH exchanged PFAS and n - 1 PFCA, amongst others. Given the reactive species present (hydroxyl radicals (·OH), hydrogen radicals (·H) and aqueous electrons (e-aq)), and the degradation products formed it was shown that aqueous electrons were the key reactive species responsible for initial PFAS degradation. Most importantly, based on degradation product formation, we found that the initial -F/+H does not have to occur at the α-fluoride (nearest the functional head group), rather occurring throughout the chain length leading to more complex degradation pathways than previously postulated. While our results support some of the reaction steps postulated in the literature, we have developed a unified 16 step and 3 pathway schematic of degradation supported by experimental observations.

Nanotoxicology research commonly utilizes pristine nanomaterials for toxicity assessment, which may not be perfectly representative of what is released into environmental systems. The goal of the present study was to develop a method to simulate human weathering of silver-containing textiles. To achieve this goal the roles of physical and chemical stress on X-Static® containing athletic textiles were investigated and compared to data collected from human weathering experiments and literature. Chemical weathering methods (artificial sweat) were used independently and alongside physical weathering methods (3D printed stretching and abrasion instruments). Non-weathered control textiles were found to release 29 ± 11 mg Ag/kg of textile into wash water effluent (ICP-MS), with 16% being released as ionic silver (ICP-MS) and the rest as metallic nanomaterials, nanosheets, and particulates of varying size (SEM/XANES). Real and simulated human weathered textiles released similar amounts of total silver (67 ± 11 mg Ag/kg, 84 ± 13 mg Ag/kg respectively) with the silver released being composed of ionic (1.5%, 2%) and a mixture of metallic and chlorinated nanomaterials, nanosheets, and particulates. The method was shown to effectively detach environmentally representative silver materials from silver-containing textiles and can provide such materials for future studies on the assessment of their fate, transport, and toxicity.

Per- and polyfluoroalkyl substances (PFAS) are manmade, fluorinated organic chemicals which have been identified as persistent organic pollutants. PFAS have surface active properties that have made them suitable for applications in oil- and water-resistant products, as well as many firefighting foams. No on-site remediation strategies exist to treat PFAS impacted soils. Mechanochemical remediation of PFOS- and PFOA-amended sand via a planetary ball mill was studied. The effect of sand mass, KOH as a co-milling reagent, and water saturation on the degradation of PFOA and PFOS was evaluated. By 4 h of milling concentrations were reduced by up to 98% for PFOS-amended dry sand and 99% for PFOA-amended dry sand without the addition of a co-milling reagent. Water saturation was determined to be a significant hindrance on the mechanochemical destruction of PFOS and PFOA. A maximum of 89% of fluoride was recovered from PFOS-amended sand when KOH was used as a co-milling reagent. It is hypothesized that reactive particles generated from the fracture of sand grains react with PFAS molecules to initiate destruction, which can result in full defluorination. Milling experiments were also conducted on soils from a Canadian firefighting training area (FFTA), demonstrating that PFOS concentrations can be reduced by up to 96% in site soils. For the first time, ball milling for the remediation of PFAS in environmental media has been demonstrated using amended sand and legacy soils from a FFTA.