Parsimonious methodology for synthesis of silver and copper functionalized cellulose.

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. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05099-7.

Retention of PFOS and PFOA Mixtures by Trapped Gas Bubbles in Porous Media.

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.

Remediation of PFAS-Contaminated Soil and Granular Activated Carbon by Smoldering Combustion.

This study explored smoldering combustion for remediating polyfluoroalkyl substance (PFAS)-impacted granular activated carbon (GAC) and PFAS-contaminated soil. GAC, both fresh and PFAS-loaded, was employed as the supplemental fuel supporting smoldering in mixtures with sand (≈175 mg PFAS/kg GAC-sand), with PFAS-spiked, laboratory-constructed soil (≈4 mg PFAS/kg soil), and with a PFAS-impacted field soil (≈0.2 mg PFAS/kg soil). The fate of PFAS and fluorine was quantified with soil and emission analyses, including targeted PFAS and suspect screening as well as hydrogen fluoride and total fluorine. Results demonstrated that exceeding 35 g GAC/kg soil resulted in self-sustained smoldering with temperatures exceeding 900 °C. Post-treatment PFAS concentrations of the treated soil were near (2 experiments) or below (7 experiments) detection limits (0.0004 mg/kg). Further, 44% of the initial PFAS on GAC underwent full destruction, compared to 16% of the PFAS on soil. Less than 1% of the initial PFAS contamination on GAC or soil was emitted as PFAS in the quantifiable analytical suite. Results suggest that the rest were emitted as altered, shorter-chain PFAS and volatile fluorinated compounds, which were scrubbed effectively with GAC. Total organic fluorine analysis proved useful for PFAS-loaded GAC in sand; however, analyzing soils suffered from interference from non-PFAS. Overall, this study demonstrated that smoldering has significant potential as an effective remediation technique for PFAS-impacted soils and PFAS-laden GAC.

Estimating the number of airports potentially contaminated with perfluoroalkyl and polyfluoroalkyl substances from aqueous film forming foam: A Canadian example.

Assessing the extent to which emerging contaminants (ECs) such as perfluoroalkyl and polyfluoroalkyl substances (PFAS) have been released into the environment is one of the foundations for developing effective management and remediation strategies for impacted sites. PFAS are known to have caused the contamination of soil, groundwater, and surface water as a result of aqueous film forming foam (AFFF) being accidentally or intentionally released into the environment. To date, the scope of the issue has not been evaluated in Canada. In this study we developed a framework, in the form of a decision tree, to estimate the number of potentially PFAS impacted airport sites in Canada as a result of AFFF releases. The screening process was completed using publicly available resources including airport websites, the Canadian Owners and Pilots Association website, Sky Vector, Transport Safety Board of Canada aviation investigation reports, the Aviation Safety Network website, and Google maps. The methodology presented in this study could be used to identify additional PFAS impacted sites in Canada or other jurisdictions worldwide. 2071 airport/heliport sites in Canada were investigated with indications that 152 (7%) of these sites likely have PFAS contamination as a result of the use of AFFF at firefighter training areas (FFTAs) and/or accidents where fires occurred. In addition, another 268 sites (13%) were identified as possibly impacted with PFASs primarily as a result of the location having the ability to store and dispense petroleum products, and therefore having AFFF systems onsite. Surficial geology was also identified for all sites determined to likely have PFAS contamination. An estimated 42.8% had surficial geology composed of sand, 27% had clay, 19.7% organic-based, with the remaining sites found on cryosols or rock. Methodological validation was also completed. The procedure used in this study successfully predicted occurrences of PFAS contamination at 25 sites where contamination, as a result of AFFF use, was confirmed by Canadian governmental departments. For these 25 sites, the distance from potential release areas to the nearest surface water was calculated. Five of the sites were within 200 meters of surface water, 19 were within one kilometer, and all 25 were within 2.5 kilometers. This suggests that surface water may have been historically impacted by PFAS at as many as 152 to 420 different airport locations in Canada.

Long-Term Field Study of Microbial Community and Dechlorinating Activity Following Carboxymethyl Cellulose-Stabilized Nanoscale Zero-Valent Iron Injection.

Nanoscale zerovalent iron (nZVI) is an emerging technology for the remediation of contaminated sites. However, there are concerns related to the impact of nZVI on in situ microbial communities. In this study, the microbial community composition at a contaminated site was monitored over two years following the injection of nZVI stabilized with carboxymethyl cellulose (nZVI-CMC). Enhanced dechlorination of chlorinated ethenes to nontoxic ethene was observed long after the expected nZVI oxidation. The abundance of Dehalococcoides (Dhc) and vinyl chloride reductase (vcrA) genes, monitored using qPCR, increased by over an order of magnitude in nZVI-CMC-impacted wells. The entire microbial community was tracked using 16S rRNA gene amplicon pyrosequencing. Following nZVI-CMC injection, a clear shift in microbial community was observed, with most notable increases in the dechlorinating genera Dehalococcoides and Dehalogenimonas. This study suggests that coupled abiotic degradation (i.e., from reaction with nZVI) and biotic degradation fueled by CMC led to the long-term degradation of chlorinated ethenes at this field site. Furthermore, nZVI-CMC addition stimulated dehalogenator growth (e.g., Dehalococcoides) and biotic degradation of chlorinated ethenes.

Contributions of Abiotic and Biotic Dechlorination Following Carboxymethyl Cellulose Stabilized Nanoscale Zero Valent Iron Injection.

A pilot scale injection of nanoscale zerovalent iron (nZVI) stabilized with carboxymethyl cellulose (CMC) was performed at an active field site contaminated with a range of chlorinated volatile organic compounds (cVOC). The cVOC concentrations and microbial populations were monitored at the site before and after nZVI injection. The remedial injection successfully reduced parent compound concentrations on site. A period of abiotic degradation was followed by a period of enhanced biotic degradation. Results suggest that the nZVI/CMC injection created conditions that stimulated the native populations of organohalide-respiring microorganisms. The abundance of Dehalococcoides spp. immediately following the nZVI/CMC injection increased by 1 order of magnitude throughout the nZVI/CMC affected area relative to preinjection abundance. Distinctly higher cVOC degradation occurred as a result of the nZVI/CMC injection over a 3 week evaluation period when compared to control wells. This suggests that both abiotic and biotic degradation occurred following injection.

Characterization of nZVI mobility in a field scale test.

Nanoscale zerovalent iron (nZVI) particles were injected into a contaminated sandy subsurface area in Sarnia, Ontario. The nZVI was synthesized on site, creating a slurry of 1 g/L nanoparticles using the chemical precipitation method with sodium borohydride (NaBH4) as the reductant in the presence of 0.8% wt. sodium carboxymethylcellulose (CMC) polymer to form a stable suspension. Individual nZVI particles formed during synthesis had a transmission electron microscopy (TEM) quantified particle size of 86.0 nm and dynamic light scattering (DLS) quantified hydrodynamic diameter for the CMC and nZVI of 624.8 nm. The nZVI was delivered to the subsurface via gravity injection. Peak normalized total Fe breakthrough of 71% was observed 1m from the injection well and remained above 50% for the 24 h injection period. Samples collected from a monitoring well 1 m from the injection contained nanoparticles with TEM-measured particle diameter of 80.2 nm and hydrodynamic diameter of 562.9 nm. No morphological changes were discernible between the injected nanoparticles and nanoparticles recovered from the monitoring well. Energy dispersive X-ray spectroscopy (EDS) was used to confirm the elemental composition of the iron nanoparticles sampled from the downstream monitoring well, verifying the successful transport of nZVI particles. This study suggests that CMC stabilized nZVI can be transported at least 1 m to the contaminated source zone at significant Fe(0) concentrations for reaction with target contaminants.

Influence of long term irrigation with pulp and paper mill effluent on the bacterial community structure and catabolic function in soil.

Microbial communities play a vital role in maintaining soil health. A multiphasic approach to assess the effect of pulp and paper mill effluent on both the structure and function of microbial soil communities is taken. Bacterial communities from agricultural soils irrigated with pulp and paper mill effluent were compared to communities form soils irrigated with well water. Samples were taken from fields in the state of Uttarakhand, India, where pulp and paper mill effluent has been used for irrigation for over 25 years. Comparisons of bacterial community structure were conducted using sequencing of the 16S rRNA gene from both isolates and clone libraries attained from the soil. Community-level physiological profiling was used to characterize the functional diversity and catabolic profile of the bacterial communities. The multiphasic approach using both physiological and molecular techniques proved to be a powerful tool in evaluating the soil bacterial community population and population differences therein. A significant and consistent difference in the population structure and function was found for the bacterial communities from soil irrigated with effluent in comparison to fields irrigated with well water. The diversity index parameters indicated that the microbial community in pulp and paper mill effluent irrigated fields were more diverse in both structure and function. This suggests that the pulp and paper mill effluent is not having a negative effect on the soil microbial community, but in fact may have a positive influence. In terms of soil health, this finding supports the continued use of pulp and paper mill effluent for irrigation. This is however only one aspect of soil health which was evaluated. Further studies on soil resistance and robustness could be undertaken to holistically evaluate soil health in this situation.

Advancing PFAS characterization: Development and optimization of a UV-H2O2-TOP assay for improved PFCA chain length preservation and organic matter tolerance.

As per- and 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-H2O2-TOP assay, identifying optimal parameters such as pH (5-9), oxidant concentration (500 mM H2O2), activation rate (63 mM H2O2 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-H2O2-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.

Mechanochemical degradation of per- and polyfluoroalkyl substances in soil using an industrial-scale horizontal ball mill with comparisons of key operational metrics.

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.

Occurrence and mobility of thiolated arsenic in legacy mine tailings.

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.

Comparison of the catabolic activity and catabolic profiles of rhizospheric, gravel-associated and interstitial microbial communities in treatment wetlands.

Microbial communities play a critical role in degrading organic contaminants in treatment wetlands; however, an understanding of the different roles played by rhizospheric, gravel-associated and interstitial microbial communities is deficient due to a lack of data directly comparing these microbial communities. Community level physiological profiling (CLPP) was used to compare the catabolic capabilities of rhizospheric, gravel-associated and interstitial microbial communities in vertical-flow planted and unplanted wetland mesocosms. Wetland mesocosms were decommissioned to gather microbial community samples associated with the roots and gravel bed media taken from the top (10 cm depth), middle (30 cm depth) and bottom (60 cm depth). The catabolic capabilities of the rhizospheric microbial communities were seen to be much greater than those of the gravel-associated communities. A decrease in catabolic capability was seen with increasing depth, suggesting that communities near the surface play a larger role in the degradation of carbon-based compounds. A general difference in catabolic profiles based on plant presence/absence was observed for the interstitial water and all gravel-associated samples at all depths, suggesting that the presence of roots within part of the mesocosm not only has a localized effect on the attached microbial population, but also on gravel-associated microbial communities throughout the mesocosms.

Elucidating the relationship between PFOA and PFOS destruction, particle size and electron generation in amended media commonly found in soils.

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.

Peaks, pores, and dragon eggs: Uncovering and quantifying the heterogeneity of treatment wetland biofilm matrices.

Biofilms serve to house diverse microbial communities, which are responsible for the majority of wastewater constituent degradation and transformation in treatment wetlands (TWs). TW biofilm has been generally conceptualized as a relatively uniform film covering available surfaces. However, no studies attaining direct visual 3D representations of biofilm morphology have been conducted. This study focuses on imaging the morphology of detached, gravel-associated, and rhizospheric (Phalaris arundinacea) biofilms from subsurface TW mesocosms. Images obtained through both traditional light microscopy, environmental scanning electron microscopy (E-SEM) and Wet-SEM revealed that TW biofilms are structurally heterogeneous ranging from corrugated films to clusters of aggregates. Features such as water channels and pores were observed suggesting that pollutant transport inside biofilms is complex, and that the interfacial surface area between water and biofilm is much larger than previously understood. Biofilm thickness generally ranged between 170 and 240 µm, with internal biofilm porosities estimated as 34 ± 10 %, reaching a maximum of 50 %. Internal biofilm matrix pore diameters ranged from 1 to 205.2 µm, with a distribution that favored pores and channels smaller than 10 µm, and a mean equivalent spherical diameter of 8.6 µm. Based on the large variation in pore and channel sizes it is expected that a variety of flow regimes and therefore pollutant dynamics are likely to occur inside TW biofilm matrices. Based on the visual evidence and analysis, a new conceptual model was created to reflect the microscale TW biofilm dynamics and morphology. This new conceptual model will serve to inform future biokinetic modelling, microscale hydrology, microbial community assessment, and pollutant treatment studies.

Forever no more: Complete mineralization of per- and polyfluoroalkyl substances (PFAS) using an optimized UV/sulfite/iodide system.

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 CC bond cleavage, and different isomers of -F/+H PFOS confirms the potential for CF 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.

Elucidating degradation mechanisms for a range of per- and polyfluoroalkyl substances (PFAS) via controlled irradiation studies.

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.

Use of a horizontal ball mill to remediate per- and polyfluoroalkyl substances in soil.

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.

Silver nanomaterials released from commercial textiles have minimal impacts on soil microbial communities at environmentally relevant concentrations.

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.

Development and validation of a method for the weathering and detachment of representative nanomaterials from conventional silver-containing textiles.

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.

A group-contribution model for predicting the physicochemical behavior of PFAS components for understanding environmental fate.

The factors controlling per- and polyfluoroalkyl substances (PFAS) environmental fate remains the subject of considerable debate and study. As surfactants, PFAS readily partition to interfaces, a property that controls their transport and fate. A group contribution model is developed to predict the extent to which PFAS partitions to the air-water interface. Langmuir adsorption and Szyszkowski equation parameters were fitted to literature air-water surface tension data for a range of PFAS and conventional hydrocarbon surfactants. This approach enabled the prediction of the impact of the hydrophilic head group, and other molecular components, on PFAS interfacial partitioning in instances when PFAS data are unavailable but analogous hydrocarbon surfactant data are available. The model was extended to predict a range of parameters (i.e., solubility, critical micelle concentration (CMC), KD, Koc and Kow) that are used to predict PFAS environmental fate, including long-range PFAS transport and in multimedia models. Model predictions were consistent with laboratory and field derived parameters reported in the literature. Additionally, the proposed model can predict the impact of pH and speciation on the extent of PFAS interfacial partitioning, a potentially important feature for understanding the behaviors of some ionizable PFAS, such as fluorinated carboxylic acids. The proposed model provides a conceptually straightforward method to predict a wide range of environmental fate parameters for a wide range of PFAS. As such, the model is a powerful tool that can be used to determine parameters needed to predict PFAS environmental fate.