ABSTRACT
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.
ABSTRACT
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.
