Effects of Monovalent Cations on the Competitive Adsorption of Perfluoroalkyl Acids by Kaolinite: Experimental Studies and Modeling
Abstract
Our hypothesis that longer-chained perfluoroalkyl acids (PFAAs) outcompete shorter-chained PFAAs during adsorption was tested in this study, wherein the adsorption interactions of six frequently detected PFAAs with kaolinite clay were modeled and examined experimentally using various suspension compositions. Competitive adsorption of PFAAs on the kaolinite surface was observed for the first time, and longer-chained PFAAs outcompeted those with a shorter chain. The electrostatic repulsion between adsorbed PFAA molecules is a primary inhibitory factor in PFAA adsorption. An increase in aqueous sodium or hydrogen ion concentration weakened electrostatic repulsions and changed the adsorption free energy. Therefore, the adsorption of a shorter-chained PFAA with weaker hydrophobicity could occur at high sodium or hydrogen ion concentrations. The experimental and modeling data suggest that the adsorption of shorter-chained PFAAs (≤4 perfluorinated carbons) in freshwater with a typical ionic strength of 10(-2.5) is not thermodynamically favorable. Furthermore, by measuring the electrokinetic potential of kaolinite suspension in the presence of PFAAs, we found that the kaolinite surface became more negatively charged because of the adsorption of PFAAs. This observation indicates that the adsorbed PFAA molecules were within the electrical double layer of the kaolinite surface and that they contributed to the potential at the slipping plane. The possible alignments of adsorbed PFAA molecules on the kaolinite surface were then proposed.
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Divalent cations may inhibit negative repulsions within the electrical double layer of the mineral surface.
“or inhibiting the negative repulsions within the electrical double layer of the mineral surface (Xiao et al., 2011).”
From Modelling the sorption behaviour of perfluoroalkyl carboxylates and perfluoroalkane sulfonates in soils (2021) · cites this paper as Xiao et al., 2011
K_MIN values increased with increasing PFAS chain length.
“K MIN values also increased with increasing PFAS chain length, a finding that is comparable to the K d increase reported for the C 7 -C 10 PFAS series on kaolinite clay (Xiao et al., 2011).”
From Modelling the sorption behaviour of perfluoroalkyl carboxylates and perfluoroalkane sulfonates in soils (2021) · cites this paper as Xiao et al., 2011
KMIN values for PFOS were higher than for PFNA.
“Furthermore, K MIN values for PFOS were higher than for PFNA, in agreement with previous observations (Xiao et al., 2011).”
From Modelling the sorption behaviour of perfluoroalkyl carboxylates and perfluoroalkane sulfonates in soils (2021) · cites this paper as Xiao et al., 2011
These KMIN values are similar to the range of Kd values (2.6-14 L/kg for PFOS and 0.5-2.3 L/kg for PFOA) obtained on pure phyllosilicate minerals such as kaolinite and montmorillonite.
“These values are similar to the range of K d values (2.6-14 L kg -1 for PFOS and 0.5-2.3L kg -1 for PFOA) obtained on pure phyllosilicate minerals such as kaolinite and montmorillonite (Jeon et al., 2011;Johnson et al., 2007;Xiao et al., 2011)”
From Modelling the sorption behaviour of perfluoroalkyl carboxylates and perfluoroalkane sulfonates in soils (2021) · cites this paper as Xiao et al., 2011
Sorption of short-chained PFASs is not thermodynamically favourable under systems with low ionic strength (1-10 mM).
“this is consistent with the hypothesis that sorption of short-chained PFASs is not thermodynamically favourable under systems with low ionic strength (1-10 mM) (Xiao et al., 2011)”
From Modelling the sorption behaviour of perfluoroalkyl carboxylates and perfluoroalkane sulfonates in soils (2021) · cites this paper as Xiao et al., 2011
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- Authors
- Xiao, F., Zhang, X., Penn, L., Gulliver, J. S., & Simcik, M. F.
- Affiliations
- University of Minnesota (US)
- Hong Kong University of Science and Technology (HK)
- Corresponding author
- Simcik, Matt F.
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-10-28
- Volume
- 45
- Issue
- 23
- Pages
- 10028-10035
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- OpenAlex
- W2327644499
- Cited by
- 272
- References
- 6
- Citations by year
- 2026: 29 · 2025: 37 · 2024: 40 · 2023: 29 · 2022: 32 · 2021: 25 · 2020: 13 · 2019: 14 · 2018: 9 · 2017: 10 · 2016: 6 · 2015: 7 · 2014: 11 · 2013: 6 · 2012: 3
- FWCI
- 5.15
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- Rare & Special e-Zone (The Hong Kong University of Science and Technology) (submittedVersion)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Water Science and Technology › Fluoride Effects and Removal
- Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
- Keywords
- perfluoroalkyl acids, competitive adsorption, kaolinite, monovalent cations, chain length effects, electrostatic repulsion, adsorption free energy, ionic strength, zeta potential, electric double layer, adsorption modeling, freshwater pollution, adsorption thermodynamics
- MeSH terms
- Adsorption, Cations, Monovalent, Fluorocarbons, Kaolin, Models, Chemical
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