Microfiltration Membrane Pore Functionalization with Primary and Quaternary Amines for PFAS Remediation: Capture, Regeneration, and Reuse

Sam Thompson; Angela M. Gutierrez; Jennifer Bukowski; Dibakar Bhattacharyya

doi:10.3390/molecules29174229

Microfiltration Membrane Pore Functionalization with Primary and Quaternary Amines for PFAS Remediation: Capture, Regeneration, and Reuse

Sam Thompson, Angela M. Gutierrez, Jennifer Bukowski, Dibakar Bhattacharyya

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The widespread production and use of multi-fluorinated carbon-based substances for a variety of purposes has contributed to the contamination of the global water supply in recent decades. Conventional wastewater treatment can reduce contaminants to acceptable levels, but the concentrated retentate stream is still a burden to the environment. A selective anion-exchange membrane capable of capture and controlled release could further concentrate necessary contaminants, making their eventual degradation or long-term storage easier. To this end, commercial microfiltration membranes were modified using pore functionalization to incorporate an anion-exchange moiety within the membrane matrix. This functionalization was performed with primary and quaternary amine-containing polymer networks ranging from weak to strong basic residues. Membrane loading ranged from 0.22 to 0.85 mmol/g membrane and 0.97 to 3.4 mmol/g membrane for quaternary and primary functionalization, respectively. Modified membranes exhibited a range of water permeances within approximately 45–131 LMH/bar. The removal of PFASs from aqueous streams was analyzed for both “long-chain” and “short-chain” analytes, perfluorooctanoic acid and perfluorobutyric acid, respectively. Synthesized membranes demonstrated as high as 90% rejection of perfluorooctanoic acid and 50–80% rejection of perfluorobutyric acid after 30% permeate recovery. Regenerated membranes maintained the capture performance for three cycles of continuous operation. The efficiency of capture and reuse can be improved through the consideration of charge density, water flux, and influent contaminant concentration. This process is not limited by the substrate and, thus, is able to be implemented on other platforms. This research advances a versatile membrane platform for environmentally relevant applications that seek to help increase the global availability of safe drinking water.

Original language	English
Article number	4229
Journal	Molecules
Volume	29
Issue number	17
DOIs	https://doi.org/10.3390/molecules29174229
State	Published - Sep 2024

Bibliographical note

Publisher Copyright:
© 2024 by the authors.

Funding

This research was supported by the National Institute of Environmental Health Sciences of the National Institute of Health under Award Number P42ES007380 and partially supported by the Southern Services Company. Jennifer Bukowski was partially supported by our NSF REU Program through NSF EPSCoR grant number 2218054. This content is solely the responsibility of the authors and does not represent the official views of the National Institute of Health, National Science Foundation, or of the Southern Services Company. The research reported in this publication was supported by the University of Kentucky Superfund Research Center as part of the National Institute of Environmental Health Sciences Superfund Research Program. We greatly appreciate the support provided by Abigail Burrows and Marissa O’Callaghan at the Mass Spectrometry and Proteomics Core (University of Kentucky) with the analysis of PFAS samples. Some of the PFAS and FTIR analyses were conducted at the SAEF (Sustainability and Analytical Equipment Facility). We thank Nicolas Briot for support with electron microscopy imaging and sample preparation at the Electron Microscopy Center. We also thank Benjamin Weaver and Selecta for providing the PVDF microfiltration membranes. Finally, we appreciate the intellectual feedback and experimental training provided by Francisco Léniz-Pizarro and Rollie Mills.

Funders	Funder number
National Science Foundation Arctic Social Science Program
University of Kentucky (UK) Superfund Research Center
National Institutes of Health/National Institute of Environmental Health Sciences
Southern Company Services, Inc.
National Institutes of Health (NIH)	P42ES007380
Office of Experimental Program to Stimulate Competitive Research	2218054

Keywords

PFAS sorption
in situ functionalization
polyether sulfone
polyvinylidene difluoride
quaternary and primary amines
responsive membrane

ASJC Scopus subject areas

Analytical Chemistry
Chemistry (miscellaneous)
Molecular Medicine
Pharmaceutical Science
Drug Discovery
Physical and Theoretical Chemistry
Organic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.3390/molecules29174229

Cite this

@article{8d8607510bd34fa9bf9f240de9631b0e,

title = "Microfiltration Membrane Pore Functionalization with Primary and Quaternary Amines for PFAS Remediation: Capture, Regeneration, and Reuse",

abstract = "The widespread production and use of multi-fluorinated carbon-based substances for a variety of purposes has contributed to the contamination of the global water supply in recent decades. Conventional wastewater treatment can reduce contaminants to acceptable levels, but the concentrated retentate stream is still a burden to the environment. A selective anion-exchange membrane capable of capture and controlled release could further concentrate necessary contaminants, making their eventual degradation or long-term storage easier. To this end, commercial microfiltration membranes were modified using pore functionalization to incorporate an anion-exchange moiety within the membrane matrix. This functionalization was performed with primary and quaternary amine-containing polymer networks ranging from weak to strong basic residues. Membrane loading ranged from 0.22 to 0.85 mmol/g membrane and 0.97 to 3.4 mmol/g membrane for quaternary and primary functionalization, respectively. Modified membranes exhibited a range of water permeances within approximately 45–131 LMH/bar. The removal of PFASs from aqueous streams was analyzed for both “long-chain” and “short-chain” analytes, perfluorooctanoic acid and perfluorobutyric acid, respectively. Synthesized membranes demonstrated as high as 90\% rejection of perfluorooctanoic acid and 50–80\% rejection of perfluorobutyric acid after 30\% permeate recovery. Regenerated membranes maintained the capture performance for three cycles of continuous operation. The efficiency of capture and reuse can be improved through the consideration of charge density, water flux, and influent contaminant concentration. This process is not limited by the substrate and, thus, is able to be implemented on other platforms. This research advances a versatile membrane platform for environmentally relevant applications that seek to help increase the global availability of safe drinking water.",

keywords = "PFAS sorption, in situ functionalization, polyether sulfone, polyvinylidene difluoride, quaternary and primary amines, responsive membrane",

author = "Sam Thompson and Gutierrez, \{Angela M.\} and Jennifer Bukowski and Dibakar Bhattacharyya",

note = "Publisher Copyright: {\textcopyright} 2024 by the authors.",

year = "2024",

month = sep,

doi = "10.3390/molecules29174229",

language = "English",

volume = "29",

number = "17",

}

TY - JOUR

T1 - Microfiltration Membrane Pore Functionalization with Primary and Quaternary Amines for PFAS Remediation

T2 - Capture, Regeneration, and Reuse

AU - Thompson, Sam

AU - Gutierrez, Angela M.

AU - Bukowski, Jennifer

AU - Bhattacharyya, Dibakar

PY - 2024/9

Y1 - 2024/9

N2 - The widespread production and use of multi-fluorinated carbon-based substances for a variety of purposes has contributed to the contamination of the global water supply in recent decades. Conventional wastewater treatment can reduce contaminants to acceptable levels, but the concentrated retentate stream is still a burden to the environment. A selective anion-exchange membrane capable of capture and controlled release could further concentrate necessary contaminants, making their eventual degradation or long-term storage easier. To this end, commercial microfiltration membranes were modified using pore functionalization to incorporate an anion-exchange moiety within the membrane matrix. This functionalization was performed with primary and quaternary amine-containing polymer networks ranging from weak to strong basic residues. Membrane loading ranged from 0.22 to 0.85 mmol/g membrane and 0.97 to 3.4 mmol/g membrane for quaternary and primary functionalization, respectively. Modified membranes exhibited a range of water permeances within approximately 45–131 LMH/bar. The removal of PFASs from aqueous streams was analyzed for both “long-chain” and “short-chain” analytes, perfluorooctanoic acid and perfluorobutyric acid, respectively. Synthesized membranes demonstrated as high as 90% rejection of perfluorooctanoic acid and 50–80% rejection of perfluorobutyric acid after 30% permeate recovery. Regenerated membranes maintained the capture performance for three cycles of continuous operation. The efficiency of capture and reuse can be improved through the consideration of charge density, water flux, and influent contaminant concentration. This process is not limited by the substrate and, thus, is able to be implemented on other platforms. This research advances a versatile membrane platform for environmentally relevant applications that seek to help increase the global availability of safe drinking water.

AB - The widespread production and use of multi-fluorinated carbon-based substances for a variety of purposes has contributed to the contamination of the global water supply in recent decades. Conventional wastewater treatment can reduce contaminants to acceptable levels, but the concentrated retentate stream is still a burden to the environment. A selective anion-exchange membrane capable of capture and controlled release could further concentrate necessary contaminants, making their eventual degradation or long-term storage easier. To this end, commercial microfiltration membranes were modified using pore functionalization to incorporate an anion-exchange moiety within the membrane matrix. This functionalization was performed with primary and quaternary amine-containing polymer networks ranging from weak to strong basic residues. Membrane loading ranged from 0.22 to 0.85 mmol/g membrane and 0.97 to 3.4 mmol/g membrane for quaternary and primary functionalization, respectively. Modified membranes exhibited a range of water permeances within approximately 45–131 LMH/bar. The removal of PFASs from aqueous streams was analyzed for both “long-chain” and “short-chain” analytes, perfluorooctanoic acid and perfluorobutyric acid, respectively. Synthesized membranes demonstrated as high as 90% rejection of perfluorooctanoic acid and 50–80% rejection of perfluorobutyric acid after 30% permeate recovery. Regenerated membranes maintained the capture performance for three cycles of continuous operation. The efficiency of capture and reuse can be improved through the consideration of charge density, water flux, and influent contaminant concentration. This process is not limited by the substrate and, thus, is able to be implemented on other platforms. This research advances a versatile membrane platform for environmentally relevant applications that seek to help increase the global availability of safe drinking water.

KW - PFAS sorption

KW - in situ functionalization

KW - polyether sulfone

KW - polyvinylidene difluoride

KW - quaternary and primary amines

KW - responsive membrane

UR - https://www.scopus.com/pages/publications/85204150475

UR - https://www.scopus.com/inward/citedby.url?scp=85204150475&partnerID=8YFLogxK

U2 - 10.3390/molecules29174229

DO - 10.3390/molecules29174229

M3 - Article

C2 - 39275076

AN - SCOPUS:85204150475

SN - 1420-3049

VL - 29

JO - Molecules

JF - Molecules

IS - 17

M1 - 4229

ER -

Microfiltration Membrane Pore Functionalization with Primary and Quaternary Amines for PFAS Remediation: Capture, Regeneration, and Reuse

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this