Adsorption, Structure, and Dynamics of Short- and Long-Chain PFAS Molecules in Kaolinite: Molecular-Level Insights
Abstract
The ubiquitous presence of poly- and perfluoroalkyl substances (PFAS) in different natural settings poses a serious threat to environmental and human health. Soils and sediments represent one of the important exposure pathways of PFAS for humans and animals. With increasing bioaccumulation and mobility, it is extremely important to understand the interactions of PFAS molecules with the dominant constituents of soils such as clay minerals. This study reports for the first time the fundamental molecular-level insights into the adsorption, interfacial structure, and dynamics of short- and long-chain PFAS molecules at the water-saturated mesopores of kaolinite clay using classical molecular dynamics (MD) simulations. At environmental conditions, all the PFAS molecules are exclusively adsorbed near the hydroxyl surface of the kaolinite, irrespective of the terminal functional groups and metal cations. The interfacial adsorption structures and coordination environments of PFAS are strongly dependent on the nature of the functional groups and their hydrophobic chain length. The formation of large, aggregated clusters of long-chain PFAS at the hydroxyl surface of kaolinite is responsible for their restricted dynamics in comparison to short-chain PFAS molecules. Such comprehensive knowledge of PFAS at the clay mineral interface is critical to developing novel site-specific degradation and mitigation strategies.
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Long-chain PFAAs, such as PFOA, tend to form large clusters on kaolinite clay surfaces due to hydrophobic interactions and direct binding between the PFAA molecules and surface hydroxyl groups.
“For example, long-chain PFAAs, such as PFOA, tend to form large clusters on kaolinite clay surfaces due to hydrophobic interactions and direct binding between the PFAA molecules and surface hydroxyl groups [159].”
From Industrial Applications, Environmental Fate, Human Exposure, and Health Effects of PFAS (2025) · cites this paper as [159]
Short-chain PFAAs, like PFBS, do not form aggregates but still experience limited movement because their terminal functional groups interact directly with soil hydroxyl groups, particularly in soils rich in kaolinite.
“In contrast, shortchain PFAAs, like PFBS, do not form aggregates but still experience limited movement because their terminal functional groups (e.g., COO -/SO3 -) interact directly with soil hydroxyl groups, particularly in soils rich in kaolinite [159].”
From Industrial Applications, Environmental Fate, Human Exposure, and Health Effects of PFAS (2025) · cites this paper as [159]
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- Authors
- Loganathan, N., & Wilson, A. K.
- Affiliations
- Michigan State University (US)
- Corresponding author
- Loganathan, Narasimhan
- Wilson, Angela K.
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2022-05-11
- Volume
- 56
- Issue
- 12
- Pages
- 8043-8052
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- OpenAlex
- W4280489538
- Cited by
- 177
- References
- 82
- Citations by year
- 2026: 59 · 2025: 60 · 2024: 32 · 2023: 20 · 2022: 6
- FWCI
- 10.45
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (CHE-2107155)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
- Physical Sciences › Engineering › Biomedical Engineering › Environmental remediation with nanomaterials
- Keywords
- per- and polyfluoroalkyl substances, PFAS adsorption, kaolinite, clay mineral surfaces, interfacial structure, molecular dynamics simulation, chain length effects, soil contamination, PFAS degradation
- MeSH terms
- Clay, Adsorption, Animals, Fluorocarbons, Humans, Kaolin, Soil
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