Per‐ and polyfluoroalkyl substances (PFAS) such as PFOS and PFOA are persistent chemicals present in the subsurface at many DoD facilities, often due to the past use of aqueous film‐forming foam (AFFF) in firefighting. PFAS pose a human health threat, necessitating feasible technologies for their removal. At present, ex situ treatment of groundwater by granular activated carbon (GAC) adsorption is the most commonly used technology for treating PFAS‐impacted water. However, this approach is very costly and relatively inefficient at removing PFOA and shorter length analogues. Ultra‐high affinity sorbents are promising for application in ex situ pump‐and‐treat adsorption systems. In addition, they offer further opportunities for in situ remedial technologies, including injection as a fine powder or use as filling in subsurface permeable adsorptive barriers.

The objective of this study is to determine the feasibility of utilizing an ultra‐high affinity sorptive remediation approach that exploits multiple, complementary bonding modes (e.g., electrostatic and hydrophobic interactions) for the remediation of PFAS‐impacted groundwater. The innovative sorbents are cationic polyaniline (PANI) and polypyrrole (PPy) polymers containing hydrophobic moieties. The unique structure of these polymeric materials enables both strong electrostatic interaction with the functional head group of anionic PFAS and hydrophobic interactions with the fluorinated tail of PFAS, allowing them to be more selective than GAC and to adsorb a wider range of compounds than anion exchange resins. By using suitable polymer precursors, the charge density and hydrophobicity of these polymers can be tailored to enhance PFAS removal.

The specific project objectives coincide with six research tasks as follows:

1. Develop and evaluate cationic hydrophobic polymers as high affinity sorbents to sequester PFAS;
2. Develop cationic hydrophobic polymers grafted on GAC and activated carbon fibers and evaluate the capacity of these composites to adsorb PFAS;
3. Evaluate the impact of co‐occurring chemical and aqueous chemistry on the sorptive removal of PFAS;
4. Assess the feasibility of regenerating cationic hydrophobic polymers;
5. Elucidate the molecular‐scale adsorption mechanisms of PFAS on the most effective engineered sorbents; and
6. With the most effective sorbents, demonstrate the continuous ex situ treatment of PFAS in groundwater and develop cost effective implementable ex situ and in situ remediation strategies for PFAS. 

Yaniv Olshansky, a postdoctoral scientist, left, and Anton Gomeniuc, an environmental engineering MS student, preparing samples for analysis at the University of Arizona as they seek to develop high-affinity adsorbents to remove PFAS from impacted water.

This project will develop novel sorbents that are highly effective at sequestering PFAS at environmentally relevant concentrations and can reliably meet the very low advisory levels established for PFOS and PFOA. The remedial processes will immobilize and highly concentrate dilute PFAS onto an adsorptive, regenerative media more efficiently and effectively than the existing technology (GAC). Benefits of this approach could include a reduction in the cost of water treatment for PFAS, reduction in the volume of waste produced, and potential applications to in situ treatment. (Anticipated Project Completion - 2023)

He, J., A. Gomeniuc, Y. Olshansky, J. Hatton, L. Abrell, J.A. Field, J. Chorover, and R. Sierra-Alvarez. 2022. Enhanced Removal of Per- And Polyfluoroalkyl Substances by Crosslinked Polyaniline Polymers. Chemical Engineering Journal, 446(5):137246. doi.org/10.1016/j.cej.2022.137246.

Olshansky, Y., A. Gomeniuc, J. Chorover, L. Abrell, J.A. Field, J. Hatton, J. He, and R. Sierra-Alvarez. 2022. Tailored Polyanilines Are High-Affinity Adsorbents for Per- and Polyfluoroalkyl Substances. ACS ES&T Water, 2(8):1402-1410. doi.org/10.1021/acsestwater.2c00166.

Olshansky, Y., A. Gomeniuc, J. Chorover, L. Abrell, J.A. Field, J. Hatton, and R. Sierra-Alvarez. 2021. Synthesis and Characterization of Customizable Polyaniline-Derived Polymers and Their Application for Perfluorooctanoic Acid Removal from Aqueous Solution. ACS ES&T Water, 1(6):1438-1446. doi.org/10.1021/acsestwater.1c00019.

Olshansky, Y., J. Chorover, L. Abrell, J.A. Field, A. Gomeniuc, J. Hatton, and R. Sierra-Alvarez. 2022. Sorption of PFAS by Cationic Hydrophobic Polymers. Abstracts of Papers of the American Chemical Society, 257. 

Theses and Dissertations

Gomeniuc, A. 2021. Novel Sorptive Approach for the Remediation of Per- and Polyfluoroalkyl Substances (PFAS) (Master’s Thesis). University of Arizona.