Increasing efficiency and treatment volumes for sonolysis of per- and poly-fluorinated substances, applied to aqueous film-forming foam.

Sonolysis of per- and polyfluoroalkyl substances (PFAS) has recently matured to field studies, treating real world contamination. However, efficient sonolysis reactor designs are poorly researched. Moreover, the variety and complexity of PFAS pollution slows reactor optimisation and scale-up. In this work, the defluorination of 10.0 mg/L aqueous perfluorooctane sulfonic acid (PFOS) was used as a model metric for the optimisation of; reactor volume (0.6 or 1.4 L), power density (100 - 350 W L-1), number of modular reactors (1-3), and liquid height (56.7 - 340 mm). Note, the ultrasonic frequency (410 kHz) and flow rate (214.2 ml min-1) was optimised in this reactor previously. Peak PFOS defluorination rate (3.40 µmolL-1 min-1) occurred at 141.8 mm, in a 0.6 L reactor, under 200 WL-1 ultrasound. Increasing the number of transducers connected in parallel to one amplifier was able to increase treatment efficiency from 78.6 to 191.8 µmol kWh-1. The model was validated using legacy aqueous film forming foam (AFFF, 3 M FC-602 Lightwater) at different dilutions (×5, ×10, ×20 and ×100). Dilution played a role in AFFF sonolysis efficiency with optimal PFAS sonolysis rate (4.28 µmol L-1 min-1) at 20 × dilution. Overall AFFF was effectively modelled with a synthetic PFOS solution, attributed to limited matrix effects in AFFF sonolysis and high PFAS concentration (0.18-1.83 g L-1) dominated by PFOS (0.15 - 1.53 g L-1).

Flow and temporal effects on the sonolytic defluorination of perfluorooctane sulfonic acid.

The removal of per- and polyfluoroalkyl substance (PFAS) pollution from the environment is a globally pressing issue, due to some PFAS' recalcitrant, bioaccumulative, and carcinogenic nature. Destruction via ultrasonic waves (sonolysis) is a promising contender for industrialisation due to; moderate power consumption, applicability to several PFAS and sample types, and limited by-products. Liquid flow rate through an ultrasonic reactor can affect the size, shape, and spatial distribution of ultrasonic cavities and hence their chemical activity. Such effects have not been studied during PFAS sonolysis, and temporal effects have not been studied much beyond the reactant concentration. Here, the effects of varying recirculating flow rate on the ultrasonic defluorination of perfluorooctane sulfonic acid (PFOS) and implications for industrial scale up are presented. Under the ultrasonic power (200 W L-1, 2.27 W cm-2) and frequency (410 kHz) used, flow rates of 79 and 214 ml min-1 enhanced defluorination up to 14 % during 30 min of treatment. However, these effects were temporal and most significant in the initial minutes of treatment. This indicated a dynamic bubble size distribution which stabilised after around 15 min. Defluorination rates of PFOS were compared with measured potassium iodide dosimetry, calorimetry, sonoluminescence (SL), and sonochemiluminescence (SCL). Flow rates which enhanced defluorination correlated moderately with enhanced SCL and negatively impacted SL, calorimetry, and dosimetry. Effects were attributed to perturbed cavity surfaces, leading to asymmetric cavity collapse, and the possibility of enhanced solvated electron production/interaction. SL, SCL, dosimetry, and calorimetric measurements were also temporal, and each showed different times to equilibrate. Flow rates of 439 and 889 ml min-1 returned all sonochemical measurements to the levels without flow, likely due to continued collapse temperature quenching by furthered bubble asymmetry. Flow also enhanced reactor cooling, which is significant for industrial temperature control. The pump energy consumed was small (≈1.9 %) compared to that of the amplifier and chiller, hence, PFOS defluorination was more cost-effective using flow. However, the effect may be limited for the longer treatment times needed for environmental remediation.

Sonolysis of per- and poly fluoroalkyl substances (PFAS): A meta-analysis.

Human ingestion of per- and polyfluoroalkyl substances (PFAS) from contaminated food and water is linked to the development of several cancers, birth defects and other illnesses. The complete mineralisation of aqueous PFAS by ultrasound (sonolysis) into harmless inorganics has been demonstrated in many studies. However, the range and interconnected nature of reaction parameters (frequency, power, temperature etc.), and variety of reaction metrics used, limits understanding of degradation mechanisms and parametric trends. This work summarises the state-of-the-art for PFAS sonolysis, considering reaction mechanisms, kinetics, intermediates, products, rate limiting steps, reactant and product measurement techniques, and effects of co-contaminants. The meta-analysis showed that mid-high frequency (100 - 1,000 kHz) sonolysis mechanisms are similar, regardless of reaction conditions, while the low frequency (20 - 100 kHz) mechanisms are specific to oxidative species added, less well understood, and generally slower than mid-high frequency mechanisms. Arguments suggest that PFAS degradation occurs via adsorption (not absorption) at the bubble interface, followed by headgroup cleavage. Further mechanistic steps toward mineralisation remain to be proven. For the first time, complete stoichiometric reaction equations are derived for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) sonolysis, which add H2 as a reaction product and consider CO an intermediate. Fluorinated intermediate products are derived for common, and more novel PFAS, and a naming system proposed for novel perfluoroether carboxylates. The meta-analysis also revealed the transition between pseudo first and zero order PFOA/S kinetics commonly occurs at 15 - 40 µM. Optimum values of; ultrasonic frequency (300 - 500 kHz), concentration (>15 - 40 µM), temperature (≈20 °C), and pH range (3.2 - 4) for rapid PFOX degradation are derived by evaluation of prior works, while optimum values for the dilution factor applied to PFAS containing firefighting foams and applied power require further work. Rate limiting steps are debated and F- is shown to be rate enhancing, while SO42- and CO2 by products are theorised to be rate limiting. Sonolysis was compared to other PFAS destructive technologies and shown to be the only treatment which fully mineralises PFAS, degrades different PFAS in order of decreasing hydrophobicity, is parametrically well studied, and has low-moderate energy requirements (several kWh g-1 PFAS). It is concluded that sonolysis of PFAS in environmental samples would be well incorporated within a treatment train for improved efficiency.

Evaluating perfluorooctanesulfonate oxidation in permanganate systems.

Permanganate (PM) has shown to be able to oxidize a range of organic contaminants including perfluorooctane sulfonate (PFOS). However, mechanisms of PFOS removal by PM have been questioned. To provide clarity to what may be happening to PFOS in PM systems, here we evaluated the ability of PM on PFOS destruction by conducting studies similar to previous studies that reported PFOS destruction which included PM solutions and PM combined with persulfate (PS). We also evaluated if addition of various soluble catalysts could enhance PM's potential to breakdown PFOS. We observed no PFOS destruction by PM. We also show that the F- and SO42- generation reported in a published study as evidence that PM was breaking bonds in PFOS were found below or not significantly higher than reported limits of quantitation and that SO42- impurities in technical PM approach the reported SO42- levels. For PM-PS systems, heterogeneous PFOS distribution was observed when subsampling reaction vessels at different depths and "salting-out" of PFOS was evident. In addition, subsequent sonication and filtering of the samples led to the apparent disappearance of most of the PFOS, which was an artifact arising from the behavior of PFOS aggregates or potential hemi-micelle formation. Given these findings, addition of salts may have application for collecting or concentrating PFOS and other PFAAs in a remediation or water treatment strategy.