Subsurface Transport Potential of Perfluoroalkyl Acids at Aqueous Film-Forming Foam (AFFF)-Impacted Sites
Abstract
Subsurface transport potential of a suite of perfluoroalkyl acids (PFAAs) was studied in batch sorption experiments with various soils and in the presence of co-contaminants relevant to aqueous film-forming foam (AFFF)-impacted sites. Specifically, PFAA sorption to multiple soils in the presence of nonaqueous phase liquid (NAPL) and nonfluorinated AFFF surfactants was examined. This study is the first to report on sorption of perfluorobutanoate (PFBA) and perfluoropentanoate (PFPeA) (log Koc = 1.88 and 1.37, respectively) and found that sorption of these compounds does not follow the chain-length dependent trend observed for longer chain-length PFAAs. Sorption of PFBA was similar to that of perfluorooctanoate (PFOA, log Koc = 1.89). NAPL and nonfluorinated AFFF surfactants all had varying impacts on sorption of longer chain (>6 CF2 groups) PFAAs. The primary impact of NAPL was observed in low foc soil (soil A) where Freundlich n-values increased when NAPL was present. Impacts of nonfluorinated AFFF surfactants varied with surfactant and soil. The anionic surfactant sodium decyl sulfate (SDS) illicited PFAA chain-length dependent impacts in two negatively charged soils with varying foc. In soil A, Kd values for perfluoroheptanoate (PFHpA) increased 91% with SDS, whereas values for perfluorodecanoate (PFDA) increased only 28%. An amphoteric surfactant, n,n-dimethyldodecylamine n-oxide (AO), had the most notable impact on PFAA sorption to a positively charged soil (soil C). In this soil, AO oxide significantly increased sorption for the longer chain PFAAs (i.e., 528% increase in Kd for PFDA). Changes in sorption caused by SDS and AO may be due to mixed hemimicelle formation, competitive sorption, or changes to PFAA solubility. Short-chain PFAA behavior in the presence of NAPL, SDS, and AO was again notable. Co-contaminants generally increased the sorption of these compounds to all soils. Log Kd values of PFBA in soil A increased 85%, 372%, and 32% in the presence of NAPL, SDS, and AO, respectively. Use of Kd values to calculate retardation factors (Rf) of PFAAs demonstrates the variability of co-contaminant impacts on PFAA transport. Whereas NAPL and nonfluorinated surfactants decreased the sorption of perfluorooctanesulfonate (PFOS) at lower PFOS concentrations (1 μg/L), they led to increases in sorption at higher PFOS concentrations (500 μg/L). These results demonstrate that PFAA groundwater transport will depend on the solid phase characteristics as well as PFAA concentration and chain length. Detailed site-specific information will likely be needed to accurately predict PFAA transport at AFFF-impacted sites.
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Koc values for PFASs between sediment and water in this study agreed well with earlier studies.
“However, the Koc values of PFASs between sediment and water obtained in this study were in good accordance with many previous researches.”
From Short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a turbid river (2016) · cites this paper as Guelfo and Higgins, 2013
The log Koc of PFBA between sediment and water in this study was comparable to the value of 1.88 from a batch sorption experiment.
“For example, the log Koc values of PFBA between sediment and water in this study were comparable to those (1.88) in a batch sorption experiment (Guelfo and Higgins, 2013).”
From Short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a turbid river (2016) · cites this paper as Guelfo and Higgins, 2013
The presence of NAPLs decreased sorption of PFOS at low PFOS concentrations (1 μg/L) but caused an increase in sorption at higher concentrations (500 ug/L).
“Guelfo and Higgins (2013) observed in batch sorption experiments that the presence of NAPLs decreased the sorption of PFOS at low PFOS concentrations (1 µg/L) but caused an increase in sorption at higher concentrations (500 ug/L).”
From Model-based identification of vadose zone controls on PFAS mobility under semi-arid climate conditions (2022) · cites this paper as Guelfo and Higgins (2013)
The N values determined in this study for PFOS and PFOA are consistent with the literature values.
“Overall, the N values determined in this study for PFOS and PFOA are consistent with the literature values.”
From Column versus batch methods for measuring PFOS and PFOA sorption to geomedia (2021) · cites this paper as Guelfo and Higgins (2013)
PFHpA is the only UCMR3 PFAS that exhibits weak sorption similar to PFBS; although it has higher occurrence and average concentration in groundwater, differences were minor compared to other groundwater-dominant PFASs.
“PFHpA is the only UCMR3 PFAS that exhibits weak sorption similar to that of PFBS (Guelfo and Higgins 2013), and though it has higher occurrence and average concentration in groundwater, the differences were minor as compared to the segregation by source water type seen for other groundwater dominant PFASs.”
From Evaluation of a national data set for insights into sources, composition, and concentrations of per- and polyfluoroalkyl substances (PFASs) in U.S. drinking water (2018) · cites this paper as Guelfo and Higgins 2013
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Self-citation
- Authors
- Guelfo, J. L., & Higgins, C. P.
- Affiliations
- Colorado School of Mines (US)
- Corresponding author
- Higgins, Christopher P.
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-04-25
- Volume
- 47
- Issue
- 9
- Pages
- 4164-4171
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- OpenAlex
- W2026492621
- Cited by
- 436
- References
- 3
- Citations by year
- 2026: 42 · 2025: 52 · 2024: 51 · 2023: 56 · 2022: 54 · 2021: 57 · 2020: 31 · 2019: 22 · 2018: 21 · 2017: 20 · 2016: 8 · 2015: 10 · 2014: 9 · 2013: 2
- FWCI
- 7.71
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Strategic Environmental Research and Development Program
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Environmental Engineering › Groundwater flow and contamination studies
- Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
- Keywords
- perfluoroalkyl acids, aqueous film-forming foam, subsurface transport, soil sorption, non-aqueous phase liquids, sodium decyl sulfate, zwitterionic surfactants, perfluorooctanoic acid, perfluorohexanoic acid, co-contamination, Freundlich isotherm, soil organic carbon
- MeSH terms
- Caprylates, Chromatography, Liquid, Decanoic Acids, Fluorocarbons, Heptanes, Hydrocarbons, Fluorinated, Quality Control, Surface-Active Agents, Water, Water Pollutants, Chemical, Tandem Mass Spectrometry
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