Distribution and release of PFAS from AFFF-impacted asphalt: How does it compare to concrete?

Aqueous film forming foam (AFFF)-impacted asphalt and concrete may serve as potential secondary sources of per- and polyfluoroalkyl substances (PFAS) to the environment through surficial leaching. We aimed to understand the vertical distribution and surficial release of PFAS from AFFF-impacted asphalt and concrete cores collected from various locations (∼10-70 m distance between samples). Among the PFAS analyzed, 6:2 FTS was observed as having the highest concentration in the surface layer (0 - 0.5 cm) of concrete (225 µg kg-1) and in the runoff from the concrete (2600 ng L-1). PFOS was detected at the highest concentration in the surface layer (0 - 0.5 cm) of asphalt (47 µg kg-1) and associated runoff (780 ng L-1). The total mass of PFAS released during three rainfall simulations accounts for a fraction of the total mass in the surface layer (0 - 0.5 cm), ranging from 0.10 - 9.8% and 0.078 - 2.4% for asphalt and concrete cores, respectively. Asphalt exhibited a higher release rate than concrete, demonstrated by the higher total release coefficient of PFAS (4 - 16 m-2) compared to that of concrete cores (1 - 5 m-2). These results suggested that, similar to concrete, AFFF-impacted asphalt may be a secondary source of PFAS to the environment.

Comparing the Leaching Behavior of Per- and Polyfluoroalkyl Substances from Contaminated Soils Using Static and Column Leaching Tests.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Sorbent assisted immobilisation of perfluoroalkyl acids in soils - effect on leaching and bioavailability.

Contamination of soils and groundwater with perfluoroalkyl acids (PFAAs) is widespread due to their use in aqueous film-forming foams (AFFF). In this study the effectiveness of RemBind®, a sorbent containing activated carbon and aluminium oxyhydroxides was tested, as a tool to reduce the leaching and bioavailability of 12 PFAAs in soils, by amending contaminated soils with 5-30% (by weight) of the sorbents. Batch tests were used to determine the leaching of PFAAs. Their bioavailability to earthworms and wheat grass was assessed in greenhouse microcosms. Leaching and bioavailability of PFOS was reduced by up to 99.9%, at most sorbent application rates. Lowest reduction of leaching was found for shorter perfluoroalkyl chain length chemicals. The specific formulation of RemBind®, which is available in a basic and superior formulation, as well as the application rate were parameters for increasing effectiveness of the treatment. Furthermore, differences in leaching as well as bioavailability were seen depending on the perfluoroalkyl chain length. A preliminary assessment of the long-term stability of the treatment, assessed after a three-year curing period, suggested that the sorbent continued to be effective in reducing PFAAs in leachates, thus showing the potential of this sorbent to hinder further environmental contamination.

Influences of Chemical Properties, Soil Properties, and Solution pH on Soil-Water Partitioning Coefficients of Per- and Polyfluoroalkyl Substances (PFASs).

The aim of this study was to assess the soil-water partitioning behavior of a wider range of per- and polyfluoroalkyl substances (PFASs) onto soils covering diverse soil properties. The PFASs studied include perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs), fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides (FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids (GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil-water partitioning coefficients (log Kd values) of the PFASs ranged from less than zero to approximately three, were chain-length-dependent, and were significantly linearly related to molecular weight (MW) for PFASs with MW > 350 g/mol (R2 = 0.94, p < 0.0001). Across all soils, the Kd values of all short-chain PFASs (≤5 -CF2- moieties) were similar and varied less (<0.5 log units) compared to long-chain PFASs (>0.5 to 1.5  log units) and zwitterions AmPr- and TAmPr-FHxSA (∼1.5 to 2 log units). Multiple soil properties described sorption of PFASs better than any single property. The effects of soil properties on sorption were different for anionic, nonionic, and zwitterionic PFASs. Solution pH could change both PFAS speciation and soil chemistry affecting surface complexation and electrostatic processes. The Kd values of all PFASs increased when solution pH decreased from approximately eight to three. Short-chain PFASs were less sensitive to solution pH than long-chain PFASs. The results indicate the complex interactions of PFASs with soil surfaces and the need to consider both PFAS type and soil properties to describe mobility in the environment.

Leaching and bioavailability of selected perfluoroalkyl acids (PFAAs) from soil contaminated by firefighting activities.

Historical usage of aqueous film-forming foam (AFFF) at firefighting training grounds (FTGs) is a potential source of perfluoroalkyl acids (PFAAs) to the surrounding environment. In this study the leaching of PFAAs from field contaminated soil and their uptake into biota was investigated. Soil was sampled from FTGs at two airports and the total as well as the leachable concentration of 12 PFAAs was determined. A greenhouse study was carried out to investigate the uptake of PFAAs from soils into earthworms (Eisenia fetida) and wheat grass (Elymus scaber). Perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) were the most dominant PFAAs in all soils samples, with concentrations of PFOS reaching 13,400 ng/g. Leachable concentrations of PFOS and PFHxS reached up to 550 µg/L and 22 µg/L, respectively. In earthworms concentrations of PFOS reached 65,100 ng/g after a 28-day exposure period, while in wheat grass the highest concentration was measured for uptake of PFHxS (2,800 ng/g) after a 10-week growth-period. Bioaccumulation factors (BAFs) for earthworms ranged from 0.1 for perfluorohexanoic acid (PFHxA) to 23 for perfluorododecanoic acid (PFDoA) and initially showed a decreasing trend with increasing perfluoroalkyl chain length, followed by an increase with increasing perfluoroalkyl chain length for perfluoroalkyl carboxylic acids (PFCAs). In wheat grass the highest BAF was found for perfluorobutanoic acid (BAF = 70), while the lowest was observed for perfluorononanoic acid (BAF = 0.06). BAFs in wheat grass decreased with increasing perfluoroalkyl chain length for both PFCAs and perfluoroalkyl sulfonic acids (PFSAs). The results show that PFAAs readily leach from impacted soils and are bioaccumulated into earthworms and plants in an analyte dependent way. This shows considerable potential for PFAAs to move away from the original source either by leaching or uptake into ecological receptors, which may be a potential entry route into the terrestrial foodweb.