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==PFAS Treatment by Anion Exchange==  
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==PFAS Destruction by Ultraviolet/Sulfite Treatment==  
 
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The ultraviolet (UV)/sulfite based reductive defluorination process has emerged as an effective and practical option for generating hydrated electrons (''e<sub><small>aq</small></sub><sup><big>'''-'''</big></sup>'' ) which can destroy [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] in water. It offers significant advantages for PFAS destruction, including significant defluorination, high treatment efficiency for long-, short-, and ultra-short chain PFAS without mass transfer limitations, selective reactivity by hydrated electrons, low energy consumption, low capital and operation costs, and no production of harmful byproducts. A UV/sulfite treatment system designed and developed by Haley and Aldrich (EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor">Haley and Aldrich, Inc. (commercial business), 2024. EradiFluor. [https://www.haleyaldrich.com/about-us/applied-research-program/eradifluor/ Comercial Website]</ref>) has been demonstrated in two field demonstrations in which it achieved near-complete defluorination and greater than 99% destruction of 40 PFAS analytes measured by EPA method 1633.
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| colspan="3" |<span style="line-height: 1em;">'''Editor-in-Chief'''<br /><span style="line-height: 1.2em;">[[Dr. Robert Borden, P.E.|Robert C. Borden, PhD, PE]]
 
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||'''Editors'''
 
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||<span style="line-height: 1.1em;">[[Dr. Jason Barnes|Jason Barnes, PhD]]<br />Cascadia College || ||[[Dr. Samuel Beal|Samuel Beal, PhD]]<br />CRREL Research and Development Center
 
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||<span style="line-height: 1.1em;">[[Craig E. Divine, Ph.D., PG|Craig E. Divine, PhD, PG]]<br />Arcadis || ||[[Dr. Kevin Finneran|Kevin Finneran, PhD]]<br />Finneran Environmental, LLC
 
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||<span style="line-height: 1.1em;">[[Dr. Upal Ghosh|Upal Ghosh, PhD]]<br />University of Maryland, Baltimore County || ||[[Dr. Rao Kotamarthi| Rao Kotamarthi, PhD]]<br />Argonne National Lab
 
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||<span style="line-height: 1.1em;">[[Kim Matthews| Kim Matthews]]<br />RTI International || ||[[Dr. Charles Newell, P.E.|Charles Newell, PhD, PE]]<br />GSI Environmental
 
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||<span style="line-height: 1.1em;"> [[Dr. Alexandra Salter-Blanc|Alexandra Salter-Blanc, PhD]]<br />Jacobs || ||[[Dr. John Wilson|John Wilson, PhD]]<br />Scissortail Environmental Solutions, LLC
 
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| style="padding:2px; width:400px;" |<h2 id="mp-otd-h2_2" style="margin:3px; background:#cedff2; font-family:inherit; font-size:120%; font-weight:bold; border:1px solid #a3b0bf; text-align:left; color:#000; padding:0.2em 0.4em;">Development&nbsp;Team&nbsp;&nbsp;</h2>
 
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|'''Executive Editor'''
 
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| [[Dr. Bilgen Yuncu, P.E. | Bilgen Yuncu, PhD, PE]]
 
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|TRC, Cary NC
 
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|''Technical Editor''
 
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|Jim Hurley, MS, EIT
 
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|TRC, Cary NC
 
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|''Administrative Assistant''
 
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|Debra Tabron
 
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|TRC, Cary NC
 
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[[Wikipedia: Ion exchange | Anion exchange]] has emerged as one of the most effective and economical technologies for treatment of water contaminated by [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | per- and polyfluoroalkyl substances (PFAS)]]. Anion exchange resins (AERs) are polymer beads (0.5–1 mm diameter) incorporating cationic adsorption sites that attract anionic PFAS by a combination of electrostatic and hydrophobic mechanisms. Both regenerable and single-use resin treatment systems are being investigated, and results from pilot-scale studies show that AERs can treat much greater volumes of PFAS-contaminated water than comparable amounts of [[Wikipedia: Activated carbon | granular activated carbon (GAC)]] adsorbent media. Life cycle treatment costs and environmental impacts of anion exchange and other adsorbent technologies are highly dependent upon the treatment criteria selected by site managers to determine when media is exhausted and requires replacement or regeneration.
 
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
 
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*[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
 
*[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
 +
*[[PFAS Ex Situ Water Treatment]]
 
*[[PFAS Sources]]
 
*[[PFAS Sources]]
*[[PFAS Transport and Fate]]
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*[[PFAS Treatment by Electrical Discharge Plasma]]
*[[PFAS Ex Situ Water Treatment]]
 
 
*[[Supercritical Water Oxidation (SCWO)]]
 
*[[Supercritical Water Oxidation (SCWO)]]
*[[PFAS Treatment by Electrical Discharge Plasma]]
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*[[Photoactivated Reductive Defluorination - PFAS Destruction]]
  
'''Contributor(s):'''  
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'''Contributors:''' John Xiong, Yida Fang, Raul Tenorio, Isobel Li, and Jinyong Liu
  
*Dr. Timothy J. Strathmann
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'''Key Resources:'''
*Dr. Anderson Ellis
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*Defluorination of Per- and Polyfluoroalkyl Substances (PFAS) with Hydrated Electrons: Structural Dependence and Implications to PFAS Remediation and Management<ref name="BentelEtAl2019">Bentel, M.J., Yu, Y., Xu, L., Li, Z., Wong, B.M., Men, Y., Liu, J., 2019. Defluorination of Per- and Polyfluoroalkyl Substances (PFASs) with Hydrated Electrons: Structural Dependence and Implications to PFAS Remediation and Management. Environmental Science and Technology, 53(7), pp. 3718-28. [https://doi.org/10.1021/acs.est.8b06648 doi: 10.1021/acs.est.8b06648]&nbsp; [[Media: BentelEtAl2019.pdf | Open Access Article]]</ref>
*Dr. Treavor H. Boyer
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*Accelerated Degradation of Perfluorosulfonates and Perfluorocarboxylates by UV/Sulfite + Iodide: Reaction Mechanisms and System Efficiencies<ref>Liu, Z., Chen, Z., Gao, J., Yu, Y., Men, Y., Gu, C., Liu, J., 2022. Accelerated Degradation of Perfluorosulfonates and Perfluorocarboxylates by UV/Sulfite + Iodide: Reaction Mechanisms and System Efficiencies. Environmental Science and Technology, 56(6), pp. 3699-3709. [https://doi.org/10.1021/acs.est.1c07608 doi: 10.1021/acs.est.1c07608]&nbsp; [[Media: LiuZEtAl2022.pdf | Open Access Article]]</ref>
 
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*Destruction of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous Film-Forming Foam (AFFF) with UV-Sulfite Photoreductive Treatment<ref>Tenorio, R., Liu, J., Xiao, X., Maizel, A., Higgins, C.P., Schaefer, C.E., Strathmann, T.J., 2020. Destruction of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF) with UV-Sulfite Photoreductive Treatment. Environmental Science and Technology, 54(11), pp. 6957-67. [https://doi.org/10.1021/acs.est.0c00961 doi: 10.1021/acs.est.0c00961]</ref>
'''Key Resource(s):'''
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*EradiFluor<sup>TM</sup><ref name="EradiFluor"/>
 
 
*Anion Exchange Resin Removal of Per- and Polyfluoroalkyl Substances (PFAS) from Impacted Water: A Critical Review<ref name="BoyerEtAl2021a">Boyer, T.H., Fang, Y., Ellis, A., Dietz, R., Choi, Y.J., Schaefer, C.E., Higgins, C.P., Strathmann, T.J., 2021. Anion Exchange Resin Removal of Per- and Polyfluoroalkyl Substances (PFAS) from Impacted Water: A Critical Review. Water Research, 200, Article 117244. [https://doi.org/10.1016/j.watres.2021.117244 doi: 10.1016/j.watres.2021.117244]&nbsp;&nbsp; [[Special:FilePath/BoyerEtAl2021a.pdf| Open Access Manuscript.pdf]]</ref>
 
 
 
*Regenerable Resin Sorbent Technologies with Regenerant Solution Recycling for Sustainable Treatment of PFAS; SERDP Project ER18-1063 Final Report<ref>Strathmann, T.J., Higgins, C.P., Boyer, T., Schaefer, C., Ellis, A., Fang, Y., del Moral, L., Dietz, R., Kassar, C., Graham, C, 2023. Regenerable Resin Sorbent Technologies with Regenerant Solution Recycling for Sustainable Treatment of PFAS; SERDP Project ER18-1063 Final Report. 285 pages. [https://serdp-estcp.org/projects/details/d3ede38b-9f24-4b22-91c9-1ad634aa5384 Project Website]&nbsp;&nbsp; [[Special:FilePath/ER18-1063.pdf| Report.pdf]]</ref>
 
  
 
==Introduction==
 
==Introduction==
[[File:StrathmannFig1.png | thumb |300px|Figure 1. Illustration of PFAS adsorption by anion exchange resins (AERs). Incorporation of longer alkyl group side chains on the cationic quaternary amine functional groups leads to PFAS-resin hydrophobic interactions that increase resin selectivity for PFAS over inorganic anions like Cl<sup>-</sup>.]]
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The hydrated electron (''e<sub><small>aq</small></sub><sup><big>'''-'''</big></sup>'' ) can be described as an electron in solution surrounded by a small number of water molecules<ref name="BuxtonEtAl1988">Buxton, G.V., Greenstock, C.L., Phillips Helman, W., Ross, A.B., 1988. Critical Review of Rate Constants for Reactions of Hydrated Electrons, Hydrogen Atoms and Hydroxyl Radicals (⋅OH/⋅O-) in Aqueous Solution. Journal of Physical and Chemical Reference Data, 17(2), pp. 513-886. [https://doi.org/10.1063/1.555805 doi: 10.1063/1.555805]</ref>. Hydrated electrons can be produced by photoirradiation of solutes, including sulfite, iodide, dithionite, and ferrocyanide, and have been reported in literature to effectively decompose per- and polyfluoroalkyl substances (PFAS) in water. The hydrated electron is one of the most reactive reducing species, with a standard reduction potential of about −2.9 volts. Though short-lived, hydrated electrons react rapidly with many species having more positive reduction potentials<ref name="BuxtonEtAl1988"/>.  
 
 
[[File:StrathmannFig2.png | thumb | 300px| Figure 2. Effect of perfluoroalkyl carbon chain length on the estimated bed volumes (BVs) to 50% breakthrough of PFCAs and PFSAs observed in a pilot study<ref name="StrathmannEtAl2020">Strathmann, T.J., Higgins, C., Deeb, R., 2020. Hydrothermal Technologies for On-Site Destruction of Site Investigation Wastes Impacted by PFAS, Final Report - Phase I. SERDP Project ER18-1501. [https://serdp-estcp.mil/projects/details/b34d6396-6b6d-44d0-a89e-6b22522e6e9c Project Website]&nbsp;&nbsp; [[Special:FilePath/ER18-1501.pdf| Report.pdf]]</ref> treating PFAS-contaminated groundwater with the PFAS-selective AER (Purolite PFA694E) ]]
 
 
 
Anion exchange is an adsorptive treatment technology that uses polymeric resin beads (0.5–1 mm diameter) that incorporate cationic adsorption sites to remove anionic pollutants from water<ref>SenGupta, A.K., 2017. Ion Exchange in Environmental Processes: Fundamentals, Applications and Sustainable Technology. Wiley. ISBN:9781119157397  [https://onlinelibrary.wiley.com/doi/book/10.1002/9781119421252 Wiley Online Library]</ref>. Anions (e.g., NO<sub>3</sub><sup>-</sup>) are adsorbed by an ion exchange reaction with anions that are initially bound to the adsorption sites (e.g., Cl<sup>-</sup>) during resin preparation. Many per- and polyfluoroalkyl substances (PFAS) of concern, including [[Wikipedia: Perfluorooctanoic acid | perfluorooctanoic acid (PFOA)]] and [[Wikipedia: Perfluorooctanesulfonic acid | perfluorooctane sulfonate (PFOS)]], are present in contaminated water as anionic species that can be adsorbed by anion exchange reactions<ref name="BoyerEtAl2021a" /><ref name="DixitEtAl2021">Dixit, F., Dutta, R., Barbeau, B., Berube, P., Mohseni, M., 2021. PFAS Removal by Ion Exchange Resins: A Review. Chemosphere, 272, Article 129777. [https://doi.org/10.1016/j.chemosphere.2021.129777 doi: 10.1016/j.chemosphere.2021.129777]</ref><ref name="RahmanEtAl2014">Rahman, M.F., Peldszus, S., Anderson, W.B., 2014. Behaviour and Fate of Perfluoroalkyl and Polyfluoroalkyl Substances (PFASs) in Drinking Water Treatment: A Review. Water Research, 50, pp. 318–340. [https://doi.org/10.1016/j.watres.2013.10.045 doi: 10.1016/j.watres.2013.10.045]</ref>.
 
<br>
 
<center><big>Anion Exchange Reaction:&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;'''PFAS<sup>-</sup>'''</big>'''<sub>(aq)</sub><big>&nbsp;+&nbsp;Cl<sup>-</sup></big><sub>(resin bound)</sub><big>&nbsp;&nbsp;&rArr;&nbsp;&nbsp;PFAS<sup>-</sup></big><sub>(resin bound)</sub><big>&nbsp;+&nbsp;Cl<sup>-</sup></big><sub>(aq)</sub>'''</center>
 
Resins most commonly applied for PFAS treatment are strong base anion exchange resins (SB-AERs) that incorporate [[Wikipedia: Quaternary ammonium cation | quaternary ammonium]] cationic functional groups with hydrocarbon side chains (R-groups) that promote PFAS adsorption by a combination of electrostatic and hydrophobic mechanisms (Figure 1)<ref name="BoyerEtAl2021a" /><ref>Fuller, Mark. Ex Situ Treatment of PFAS-Impacted Groundwater Using Ion Exchange with Regeneration; ER18-1027. [https://serdp-estcp.mil/projects/details/af660326-56e0-4d3c-b80a-1d8a2d613724 Project Website].</ref>. SB-AERs maintain cationic functional groups independent of water pH. Recently introduced ‘PFAS-selective’ AERs show >1,000,000-fold greater selectivity for some PFAS over the Cl<sup>-</sup> initially loaded onto resins<ref name="FangEtAl2021">Fang, Y., Ellis, A., Choi, Y.J., Boyer, T.H., Higgins, C.P., Schaefer, C.E., Strathmann, T.J., 2021. Removal of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF) Using Ion-Exchange and Nonionic Resins. Environmental Science and Technology, 55(8), pp. 5001–5011. [https://doi.org/10.1021/acs.est.1c00769 doi: 10.1021/acs.est.1c00769]</ref>. These resins also show much higher adsorption capacities for PFAS (mg PFAS adsorbed per gram of adsorbent media) than granular activated carbon (GAC) adsorbents.
 
 
 
PFAS of concern include a wide range of structures, including [[Wikipedia: Perfluoroalkyl carboxylic acids | perfluoroalkyl carboxylic acids (PFCAs)]] and [[Wikipedia: Perfluorosulfonic acids | perfluoroalkyl sulfonic acids (PFSAs)]] of varying carbon chain length<ref>Interstate Technology Regulatory Council (ITRC), 2023. Technical Resources for Addressing Environmental Releases of Per- and Polyfluoroalkyl Substances (PFAS). [https://pfas-1.itrcweb.org/ ITRC PFAS Website]</ref>. As such, affinity for adsorption to AERs is heavily dependent upon PFAS structure<ref name="BoyerEtAl2021a" /><ref name="DixitEtAl2021" />. In general, it has been found that the extent of adsorption increases with increasing chain length, and that PFSAs adsorb more strongly than PFCAs of similar chain length (Figure 2)<ref name="FangEtAl2021" /><ref>Gagliano, E., Sgroi, M., Falciglia, P.P., Vagliasindi, F.G.A., Roccaro, P., 2020. Removal of Poly- and Perfluoroalkyl Substances (PFAS) from Water by Adsorption: Role of PFAS Chain Length, Effect of Organic Matter and Challenges in Adsorbent Regeneration. Water Research, 171, Article 115381. [https://doi.org/10.1016/j.watres.2019.115381 doi: 10.1016/j.watres.2019.115381]</ref>. The chain length-dependence supports the conclusion that PFAS-resin hydrophobic mechanisms contribute to adsorption. Adsorption of polyfluorinated structures also depend on structure and prevailing charge, with adsorption of zwitterionic species (containing both anionic and cationic groups in the same structure) to AERs being documented despite having a net neutral charge<ref name="FangEtAl2021" />.
 
 
 
==Reactors for Treatment of PFAS-Contaminated Water==
 
Anion exchange treatment of water is accomplished by pumping contaminated water through fixed bed reactors filled with AERs (Figure 3). A common configuration involves flowing water through two reactors arranged in a lead-lag configuration<ref name="WoodardEtAl2017">Woodard, S., Berry, J., Newman, B., 2017. Ion Exchange Resin for PFAS Removal and Pilot Test Comparison to GAC. Remediation, 27(3), pp. 19–27. [https://doi.org/10.1002/rem.21515 doi: 10.1002/rem.21515]</ref>. Water flows through the pore spaces in close contact with resin beads. Sufficient contact time needs to be provided, referred to as empty bed contact time (EBCT), to allow PFAS to diffuse from the water into the resin structure and adsorb to exchange sites. Typical EBCTs for AER treatment of PFAS are 2-5 min, shorter than contact times recommended for granular activated carbon (GAC) adsorbents (≥10 min)<ref name="LiuEtAl2022">Liu, C. J., Murray, C.C., Marshall, R.E., Strathmann, T.J., Bellona, C., 2022. Removal of Per- and Polyfluoroalkyl Substances from Contaminated Groundwater by Granular Activated Carbon and Anion Exchange Resins: A Pilot-Scale Comparative Assessment. Environmental Science: Water Research and Technology, 8(10), pp. 2245–2253. [https://doi.org/10.1039/D2EW00080F doi: 10.1039/D2EW00080F]</ref><ref>Liu, C.J., Werner, D., Bellona, C., 2019. Removal of Per- and Polyfluoroalkyl Substances (PFASs) from Contaminated Groundwater Using Granular Activated Carbon: A Pilot-Scale Study with Breakthrough Modeling. Environmental Science: Water Research and Technology, 5(11), pp. 1844–1853. [https://doi.org/10.1039/C9EW00349E doi: 10.1039/C9EW00349E]</ref>. The higher adsorption capacities and shorter EBCTs of AERs enable use of much less media and smaller vessels than GAC, reducing expected capital costs for AER treatment systems<ref name="EllisEtAl2023">Ellis, A.C., Boyer, T.H., Fang, Y., Liu, C.J., Strathmann, T.J., 2023. Life Cycle Assessment and Life Cycle Cost Analysis of Anion Exchange and Granular Activated Carbon Systems for Remediation of Groundwater Contaminated by Per- and Polyfluoroalkyl Substances (PFASs). Water Research, 243, Article 120324. [https://doi.org/10.1016/j.watres.2023.120324 doi: 10.1016/j.watres.2023.120324]</ref>.  
 
 
 
Like other adsorption media, PFAS will initially adsorb to media encountered near the inlet side of the reactor, but as ion exchange sites become saturated with PFAS, the active zone of adsorption will begin to migrate through the packed bed with increasing volume of water treated. Moreover, some PFAS with lower affinity for exchange sites (e.g., shorter-chain PFAS that are less hydrophobic) will be displaced by competition from other PFAS (e.g., longer-chain PFAS that are more hydrophobic) and move further along the bed to occupy open sites<ref name="EllisEtAl2022">Ellis, A.C., Liu, C.J., Fang, Y., Boyer, T.H., Schaefer, C.E., Higgins, C.P., Strathmann, T.J., 2022. Pilot Study Comparison of Regenerable and Emerging Single-Use Anion Exchange Resins for Treatment of Groundwater Contaminated by per- and Polyfluoroalkyl Substances (PFASs). Water Research, 223, Article 119019. [https://doi.org/10.1016/j.watres.2022.119019 doi: 10.1016/j.watres.2022.119019]&nbsp;&nbsp; [[Special:FilePath/EllisEtAl2022.pdf| Open Access Manuscript]]</ref>. Eventually, PFAS will start to breakthrough into the effluent from the reactor, typically beginning with the shorter-chain compounds. The initial breakthrough of shorter-chain PFAS is similar to the behavior observed for AER treatment of inorganic contaminants.
 
 
 
Upon breakthrough, treatment is halted, and the exhausted resins are either replaced with fresh media or regenerated before continuing treatment. Most vendors are currently operating AER treatment systems for PFAS in single-use mode where virgin media is delivered to replace exhausted resins, which are transported off-site for disposal or incineration<ref name="BoyerEtAl2021a" />. As an alternative, some providers are developing regenerable AER treatment systems, where exhausted resins are regenerated on-site by desorbing PFAS from the resins using a combination of salt brine (typically ≥1 wt% NaCl) and cosolvent (typically ≥70 vol% methanol)<ref name="BoyerEtAl2021a" /><ref name="BoyerEtAl2021b">Boyer, T.H., Ellis, A., Fang, Y., Schaefer, C.E., Higgins, C.P., Strathmann, T.J., 2021. Life Cycle Environmental Impacts of Regeneration Options for Anion Exchange Resin Remediation of PFAS Impacted Water. Water Research, 207, Article 117798. [https://doi.org/10.1016/j.watres.2021.117798 doi: 10.1016/j.watres.2021.117798]&nbsp;&nbsp; [[Special:FilePath/BoyerEtAl2021b.pdf| Open Access Manuscript]]</ref><ref>Houtz, E., (projected completion 2025). Treatment of PFAS in Groundwater with Regenerable Anion Exchange Resin as a Bridge to PFAS Destruction, Project ER23-8391. [https://serdp-estcp.mil/projects/details/a12b603d-0d4a-4473-bf5b-069313a348ba/treatment-of-pfas-in-groundwater-with-regenerable-anion-exchange-resin-as-a-bridge-to-pfas-destruction Project Website].</ref>. This mode of operation allows for longer term use of resins before replacement, but requires more complex and extensive site infrastructure. Cosolvent in the resulting waste regenerant can be recycled by distillation, which reduces chemical inputs and lowers the volume of PFAS-contaminated still bottoms requiring further treatment or disposal<ref name="BoyerEtAl2021b" />. Currently, there is active research on various technologies for destruction of PFAS concentrates in AER still bottoms residuals<ref name="StrathmannEtAl2020">Strathmann, T.J., Higgins, C., Deeb, R., 2020. Hydrothermal Technologies for On-Site Destruction of Site Investigation Wastes Impacted by PFAS, Final Report - Phase I. SERDP Project ER18-1501. [https://serdp-estcp.mil/projects/details/b34d6396-6b6d-44d0-a89e-6b22522e6e9c Project Website]&nbsp;&nbsp; [[Media: ER18-1501.pdf | Report.pdf]]</ref><ref name="HuangEtAl2021">Huang, Q., Woodard, S., Nickleson, M., Chiang, D., Liang, S., Mora, R., 2021. Electrochemical Oxidation of Perfluoroalkyl Acids in Still Bottoms from Regeneration of Ion Exchange Resins Phase I - Final Report. SERDP Project ER18-1320. [https://serdp-estcp.mil/projects/details/ccaa70c4-b40a-4520-ba17-14db2cd98e8f Project Website]&nbsp;&nbsp; [[Special:FilePath/ER18-1320.pdf| Report.pdf]]</ref>.
 
 
 
==Field Demonstrations==
 
Field pilot studies are critical to demonstrating the effectiveness and expected costs of PFAS treatment technologies. A growing number of pilot studies testing the performance of commercially available AERs to treat PFAS-contaminated groundwater, including sites impacted by historical use of aqueous film-forming foam (AFFF), have been published recently (Figure 4)
 
 
 
 
 
 
 
In comparison to other reported PFAS destruction techniques, PRD offers several advantages:
 
 
 
*Relative to UV/sodium sulfite and UV/sodium iodide systems, the fitted degradation rates in the micelle-accelerated PRD reaction system were ~18 and ~36 times higher, indicating the key role of the self-assembled micelle in creating a confined space for rapid PFAS destruction<ref name="ChenEtAl2020" />. The negatively charged hydrated electron associated with the positively charged cetyltrimethylammonium ion (CTA<sup>+</sup>) forms the surfactant micelle to trap molecules with similar structures, selectively mineralizing compounds with both hydrophobic and hydrophilic groups (e.g., PFAS).
 
*The PRD reaction does not require solid catalysts or electrodes, which can be expensive to acquire and difficult to regenerate or dispose.
 
*The aqueous solution is not heated or pressurized, and the UV wavelength used does not cause direct water [[Wikipedia: Photodissociation | photolysis]], therefore the energy input to the system is more directly employed to destroy PFAS, resulting in greater energy efficiency.
 
*Since the reaction is performed at ambient temperature and pressure, there are limited concerns regarding environmental health and safety or volatilization of PFAS compared to heated and pressurized systems.
 
*Due to the reductive nature of the reaction, there is no formation of unwanted byproducts resulting from oxidative processes, such as [[Wikipedia: Perchlorate | perchlorate]]  generation during electrochemical oxidation<ref>Veciana, M., Bräunig, J., Farhat, A., Pype, M. L., Freguia, S., Carvalho, G., Keller, J., Ledezma, P., 2022. Electrochemical Oxidation Processes for PFAS Removal from Contaminated Water and Wastewater: Fundamentals, Gaps and Opportunities towards Practical Implementation. Journal of Hazardous Materials, 434, Article 128886. [https://doi.org/10.1016/j.jhazmat.2022.128886 doi: 10.1016/j.jhazmat.2022.128886]</ref><ref>Trojanowicz, M., Bojanowska-Czajka, A., Bartosiewicz, I., Kulisa, K., 2018. Advanced Oxidation/Reduction Processes Treatment for Aqueous Perfluorooctanoate (PFOA) and Perfluorooctanesulfonate (PFOS) – A Review of Recent Advances. Chemical Engineering Journal, 336, pp. 170–199. [https://doi.org/10.1016/j.cej.2017.10.153 doi: 10.1016/j.cej.2017.10.153]</ref><ref>Wanninayake, D.M., 2021. Comparison of Currently Available PFAS Remediation Technologies in Water: A Review. Journal of Environmental Management, 283, Article 111977. [https://doi.org/10.1016/j.jenvman.2021.111977 doi: 10.1016/j.jenvman.2021.111977]</ref>.
 
*Aqueous fluoride ions are the primary end products of PRD, enabling real-time reaction monitoring with a fluoride [[Wikipedia: Ion-selective electrode | ion selective electrode (ISE)]], which is far less expensive and faster than relying on PFAS analytical data alone to monitor system performance.
 
 
 
===Disadvantages===
 
 
 
*The CTAB additive is only partially consumed during the reaction, and although CTAB is not problematic when discharged to downstream treatment processes that incorporate aerobic digestors, CTAB can be toxic to surface waters and anaerobic digestors. Therefore, disposal options for treated solutions will need to be evaluated on a site-specific basis. Possible options include removal of CTAB from solution for reuse in subsequent PRD treatments, or implementation of an oxidation reaction to degrade CTAB.
 
*The PRD reaction rate decreases in water matrices with high levels of total dissolved solids (TDS). It is hypothesized that in high TDS solutions (e.g., ion exchange still bottoms with TDS of 200,000 ppm), the presence of ionic species inhibits the association of the electron donor with the micelle, thus decreasing the reaction rate.
 
*The PRD reaction rate decreases in water matrices with very low UV transmissivity. Low UV transmissivity (i.e., < 1 %) prevents the penetration of UV light into the solution, such that the utilization efficiency of UV light decreases.
 
 
 
==State of the Art==
 
 
 
===Technical Performance===
 
[[File:WittFig2.png | thumb |400px| Figure 2. Enspired Solutions<small><sup>TM</sup></small> commercial PRD PFAS destruction equipment, the PFASigator<small><sup>TM</sup></small>. Dimensions are 8 feet long by 4 feet wide by 9 feet tall.]]
 
  
{| class="wikitable mw-collapsible" style="float:left; margin-right:20px; text-align:center;"
+
Among the electron source chemicals, sulfite (SO<sub>3</sub><sup>2−</sup>) has emerged as one of the most effective and practical options for generating hydrated electrons to destroy PFAS in water. The mechanism of hydrated electron production in a sulfite solution under ultraviolet is shown in Equation 1 (UV is denoted as ''hv, SO<sub>3</sub><sup><big>'''•-'''</big></sup>'' is the sulfur trioxide radical anion):
|+Table 1. Percent decreases from initial PFAS concentrations during benchtop testing of PRD treatment in different water matrices
+
</br>
|-
+
::<big>'''Equation 1:'''</big>&nbsp;&nbsp; [[File: XiongEq1.png | 200 px]]
!Analytes
 
!
 
!GW
 
!FF
 
!AFFF<br>Rinsate
 
!AFF<br>(diluted 10X)
 
!IDW NF
 
|-
 
|&Sigma; Total PFAS<small><sup>a</sup></small> (ND=0)
 
| rowspan="9" style="background-color:white;" |<p style="writing-mode: vertical-rl">% Decrease<br>(Initial Concentration, &mu;g/L)</p>
 
|93%<br>(370)||96%<br>(32,000)||89%<br>(57,000)||86 %<br>(770,000)||84%<br>(82)
 
|-
 
|&Sigma; Total PFAS (ND=MDL)||93%<br>(400)||86%<br>(32,000)||90%<br>(59,000)||71%<br>(770,000)||88%<br>(110)
 
|-
 
|&Sigma; Total PFAS (ND=RL)||94%<br>(460)||96%<br>(32,000)||91%<br>(66,000)||34%<br>(770,000)||92%<br>(170)
 
|-
 
|&Sigma; Highly Regulated PFAS<small><sup>b</sup></small> (ND=0)||>99%<br>(180)||>99%<br>(20,000)||95%<br>(20,000)||92%<br>(390,000)||95%<br>(50)
 
|-
 
|&Sigma; Highly Regulated PFAS (ND=MDL)||>99%<br>(180)||98%<br>(20,000)||95%<br>(20,000)||88%<br>(390,000)||95%<br> (52)
 
|-
 
|&Sigma; Highly Regulated PFAS (ND=RL)||>99%<br>(190)||93%<br>(20,000)||95%<br>(20,000)||79%<br>(390,000)||95%<br>(55)
 
|-
 
|&Sigma; High Priority PFAS<small><sup>c</sup></small> (ND=0)||91%<br>(180)||98%<br>(20,000)||85%<br>(20,000)||82%<br>(400,000)||94%<br>(53)
 
|-
 
|&Sigma; High Priority PFAS (ND=MDL)||91%<br>(190)||94%<br>(20,000)||85%<br>(20,000)||79%<br>(400,000)||86%<br>(58)
 
|-
 
|&Sigma; High Priority PFAS (ND=RL)||92%<br>(200)||87%<br>(20,000)||86%<br>(21,000)||70%<br>(400,000)||87%<br>(65)
 
|-
 
|Fluorine mass balance<small><sup>d</sup></small>|| ||106%||109%||110%||65%||98%
 
|-
 
|Sorbed organic fluorine<small><sup>e</sup></small>|| ||4%||4%||33%||N/A||31%
 
|-
 
| colspan="7" style="background-color:white; text-align:left" |<small>Notes:<br>GW = groundwater<br>GW FF = groundwater foam fractionate<br>AFFF rinsate = rinsate collected from fire system decontamination<br>AFFF (diluted 10x) = 3M Lightwater AFFF diluted 10x<br>IDW NF = investigation derived waste nanofiltrate<br>ND = non-detect<br>MDL = Method Detection Limit<br>RL = Reporting Limit<br><small><sup>a</sup></small>Total PFAS = 40 analytes + unidentified PFCA precursors<br><small><sup>b</sup></small>Highly regulated PFAS = PFNA, PFOA, PFOS, PFHxS, PFBS, HFPO-DA<br><small><sup>c</sup></small>High priority PFAS = PFNA, PFOA, PFHxA, PFBA, PFOS, PFHxS, PFBS, HFPO-DA<br><small><sup>d</sup></small>Ratio of the final to the initial organic fluorine plus inorganic fluoride concentrations<br><small><sup>e</sup></small>Percent of organic fluorine that sorbed to the reactor walls during treatment<br></small>
 
|}
 
<br>
 
The&nbsp;PRD&nbsp;reaction&nbsp;has&nbsp;been validated at the bench scale for the destruction of PFAS in a variety of environmental samples from Department of Defense sites (Table 1). Enspired Solutions<small><sup>TM</sup></small> has designed and manufactured a fully automatic commercial-scale piece of equipment called PFASigator<small><sup>TM</sup></small>, specializing in PRD PFAS destruction (Figure 2). This equipment is modular and scalable, has a small footprint, and can be used alone or in series with existing water treatment trains. The PFASigator<small><sup>TM</sup></small> employs commercially available UV reactors and monitoring meters that have been used in the water industry for decades. The system has been tested on PRD efficiency operational parameters, and key metrics were proven to be consistent with benchtop studies.  
 
  
Bench scale PRD tests were performed for the following samples collected from Department of Defense sites: groundwater (GW), groundwater foam fractionate (FF), firefighting truck rinsate ([[Wikipedia: Firefighting foam | AFFF]] Rinsate), 3M Lightwater AFFF, investigation derived waste nanofiltrate (IDW NF), [[Wikipedia: Ion exchange | ion exchange]] still bottom (IX SB), and Ansulite AFFF. The PRD treatment was more effective in low conductivity/TDS solutions. Generally, PRD reaction rates decrease for solutions with a TDS > 10,000 ppm, with an upper limit of 30,000 ppm. Ansulite AFFF and IX SB samples showed low destruction efficiencies during initial screening tests, which was primarily attributed to their high TDS concentrations. Benchtop testing data are shown in Table 1 for the remaining five sample matrices.
+
The hydrated electron has demonstrated excellent performance in destroying PFAS such as [[Wikipedia:Perfluorooctanesulfonic acid | perfluorooctanesulfonic acid (PFOS)]], [[Wikipedia:Perfluorooctanoic acid|perfluorooctanoic acid (PFOA)]]<ref>Gu, Y., Liu, T., Wang, H., Han, H., Dong, W., 2017. Hydrated Electron Based Decomposition of Perfluorooctane Sulfonate (PFOS) in the VUV/Sulfite System. Science of The Total Environment, 607-608, pp. 541-48. [https://doi.org/10.1016/j.scitotenv.2017.06.197 doi: 10.1016/j.scitotenv.2017.06.197]</ref> and [[Wikipedia: GenX|GenX]]<ref>Bao, Y., Deng, S., Jiang, X., Qu, Y., He, Y., Liu, L., Chai, Q., Mumtaz, M., Huang, J., Cagnetta, G., Yu, G., 2018. Degradation of PFOA Substitute: GenX (HFPO–DA Ammonium Salt): Oxidation with UV/Persulfate or Reduction with UV/Sulfite? Environmental Science and Technology, 52(20), pp. 11728-34. [https://doi.org/10.1021/acs.est.8b02172 doi: 10.1021/acs.est.8b02172]</ref>. Mechanisms include cleaving carbon-to-fluorine (C-F) bonds (i.e., hydrogen/fluorine atom exchange) and chain shortening (i.e., [[Wikipedia: Decarboxylation | decarboxylation]], [[Wikipedia: Hydroxylation | hydroxylation]], [[Wikipedia: Elimination reaction | elimination]], and [[Wikipedia: Hydrolysis | hydrolysis]])<ref name="BentelEtAl2019"/>.
  
During treatment, PFOS and PFOA concentrations decreased 96% to >99% and 77% to 97%, respectively. For the PFAS with proposed drinking water Maximum Contaminant Levels (MCLs) recently established by the USEPA (PFNA, PFOA, PFOS, PFHxS, PFBS, and HFPO-DA), concentrations decreased >99% for GW, 93% for FF, 95% for AFFF Rinsate and IDW NF, and 79% for AFFF (diluted 10x) during the treatment time allotted. Meanwhile, the total PFAS concentrations, including all 40 known PFAS analytes and unidentified perfluorocarboxylic acid (PFCA) precursors, decreased from 34% to 96% following treatment. All of these concentration reduction values were calculated by using reporting limits (RL) as the concentrations for non-detects.
+
==Process Description==
 +
A commercial UV/sulfite treatment system designed and developed by Haley and Aldrich (EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/>) includes an optional pre-oxidation step to transform PFAS precursors (when present) and a main treatment step to break C-F bonds by UV/sulfite reduction. The effluent from the treatment process can be sent back to the influent of a pre-treatment separation system (such as a [[Wikipedia: Foam fractionation | foam fractionation]], [[PFAS Treatment by Anion Exchange | regenerable ion exchange]], or a [[Reverse Osmosis and Nanofiltration Membrane Filtration Systems for PFAS Removal | membrane filtration system]]) for further concentration or sent for off-site disposal in accordance with relevant disposal regulations. A conceptual treatment process diagram is shown in Figure 1. [[File: XiongFig1.png | thumb | left | 600 px | Figure 1: Conceptual Treatment Process for a Concentrated PFAS Stream]]<br clear="left"/>
  
Excellent fluorine/fluoride mass balance was achieved. There was nearly a 1:1 conversion of organic fluorine to free inorganic fluoride ion during treatment of GW, FF and AFFF Rinsate. The 3M Lightwater AFFF (diluted 10x) achieved only 65% fluorine mass balance, but this was likely due to high adsorption of PFAS to the reactor.
+
==Advantages==
 +
A UV/sulfite treatment system offers significant advantages for PFAS destruction compared to other technologies, including high defluorination percentage, high treatment efficiency for short-chain PFAS without mass transfer limitation, selective reactivity by ''e<sub><small>aq</small></sub><sup><big>'''-'''</big></sup>'', low energy consumption, and the production of no harmful byproducts. A summary of these advantages is provided below:
 +
*'''High efficiency for short- and ultrashort-chain PFAS:''' While the degradation efficiency for short-chain PFAS is challenging for some treatment technologies<ref>Singh, R.K., Brown, E., Mededovic Thagard, S., Holson, T.M., 2021. Treatment of PFAS-containing landfill leachate using an enhanced contact plasma reactor. Journal of Hazardous Materials, 408, Article 124452. [https://doi.org/10.1016/j.jhazmat.2020.124452 doi: 10.1016/j.jhazmat.2020.124452]</ref><ref>Singh, R.K., Multari, N., Nau-Hix, C., Woodard, S., Nickelsen, M., Mededovic Thagard, S., Holson, T.M., 2020. Removal of Poly- and Per-Fluorinated Compounds from Ion Exchange Regenerant Still Bottom Samples in a Plasma Reactor. Environmental Science and Technology, 54(21), pp. 13973-80. [https://doi.org/10.1021/acs.est.0c02158 doi: 10.1021/acs.est.0c02158]</ref><ref>Nau-Hix, C., Multari, N., Singh, R.K., Richardson, S., Kulkarni, P., Anderson, R.H., Holsen, T.M., Mededovic Thagard S., 2021. Field Demonstration of a Pilot-Scale Plasma Reactor for the Rapid Removal of Poly- and Perfluoroalkyl Substances in Groundwater. American Chemical Society’s Environmental Science and Technology (ES&T) Water, 1(3), pp. 680-87. [https://doi.org/10.1021/acsestwater.0c00170 doi: 10.1021/acsestwater.0c00170]</ref>, the UV/sulfite process demonstrates excellent defluorination efficiency for both short- and ultrashort-chain PFAS, including [[Wikipedia: Trifluoroacetic acid | trifluoroacetic acid (TFA)]] and [[Wikipedia: Perfluoropropionic acid | perfluoropropionic acid (PFPrA)]]. 
 +
*'''High defluorination ratio:''' As shown in Figure 3, the UV/sulfite treatment system has demonstrated near 100% defluorination for various PFAS under both laboratory and field conditions.
 +
*'''No harmful byproducts:''' While some oxidative technologies, such as electrochemical oxidation, generate toxic byproducts, including perchlorate, bromate, and chlorate, the UV/sulfite system employs a reductive mechanism and does not generate these byproducts.  
 +
*'''Ambient pressure and low temperature:''' The system operates under ambient pressure and low temperature (<60°C), as it utilizes UV light and common chemicals to degrade PFAS. 
 +
*'''Low energy consumption:''' The electrical energy per order values for the degradation of [[Wikipedia: Perfluoroalkyl carboxylic acids | perfluorocarboxylic acids (PFCAs)]] by UV/sulfite have been reduced to less than 1.5 kilowatt-hours (kWh) per cubic meter under laboratory conditions. The energy consumption is orders of magnitude lower than that for many other destructive PFAS treatment technologies (e.g., [[Supercritical Water Oxidation (SCWO) | supercritical water oxidation]])<ref>Nzeribe, B.N., Crimi, M., Mededovic Thagard, S., Holsen, T.M., 2019. Physico-Chemical Processes for the Treatment of Per- And Polyfluoroalkyl Substances (PFAS): A Review. Critical Reviews in Environmental Science and Technology, 49(10), pp. 866-915. [https://doi.org/10.1080/10643389.2018.1542916 doi: 10.1080/10643389.2018.1542916]</ref>.
 +
*'''Co-contaminant destruction:''' The UV/sulfite system has also been reported effective in destroying certain co-contaminants in wastewater. For example, UV/sulfite is reported to be effective in reductive dechlorination of chlorinated volatile organic compounds, such as trichloroethene, 1,2-dichloroethane, and vinyl chloride<ref>Jung, B., Farzaneh, H., Khodary, A., Abdel-Wahab, A., 2015. Photochemical degradation of trichloroethylene by sulfite-mediated UV irradiation. Journal of Environmental Chemical Engineering, 3(3), pp. 2194-2202. [https://doi.org/10.1016/j.jece.2015.07.026 doi: 10.1016/j.jece.2015.07.026]</ref><ref>Liu, X., Yoon, S., Batchelor, B., Abdel-Wahab, A., 2013. Photochemical degradation of vinyl chloride with an Advanced Reduction Process (ARP) – Effects of reagents and pH. Chemical Engineering Journal, 215-216, pp. 868-875. [https://doi.org/10.1016/j.cej.2012.11.086 doi: 10.1016/j.cej.2012.11.086]</ref><ref>Li, X., Ma, J., Liu, G., Fang, J., Yue, S., Guan, Y., Chen, L., Liu, X., 2012. Efficient Reductive Dechlorination of Monochloroacetic Acid by Sulfite/UV Process. Environmental Science and Technology, 46(13), pp. 7342-49. [https://doi.org/10.1021/es3008535 doi: 10.1021/es3008535]</ref><ref>Li, X., Fang, J., Liu, G., Zhang, S., Pan, B., Ma, J., 2014. Kinetics and efficiency of the hydrated electron-induced dehalogenation by the sulfite/UV process. Water Research, 62, pp. 220-228. [https://doi.org/10.1016/j.watres.2014.05.051 doi: 10.1016/j.watres.2014.05.051]</ref>.
  
===Application===
+
==Limitations==
Due to the first-order kinetics of PRD, destruction of PFAS is most energy efficient when paired with a pre-concentration technology, such as foam fractionation (FF), nanofiltration, reverse osmosis, or resin/carbon adsorption, that remove PFAS from water. Application of the PFASigator<small><sup>TM</sup></small> is therefore proposed as a part of a PFAS treatment train that includes a pre-concentration step.
+
Several environmental factors and potential issues have been identified that may impact the performance of the UV/sulfite treatment system, as listed below. Solutions to address these issues are also proposed.
 +
*Environmental factors, such as the presence of elevated concentrations of natural organic matter (NOM), dissolved oxygen, or nitrate, can inhibit the efficacy of UV/sulfite treatment systems by scavenging available hydrated electrons. Those interferences are commonly managed through chemical additions, reaction optimization, and/or dilution, and are therefore not considered likely to hinder treatment success.
 +
*Coloration in waste streams may also impact the effectiveness of the UV/sulfite treatment system by blocking the transmission of UV light, thus reducing the UV lamp's effective path length. To address this, pre-treatment may be necessary to enable UV/sulfite destruction of PFAS in the waste stream. Pre-treatment may include the use of strong oxidants or coagulants to consume or remove UV-absorbing constituents.
 +
*The degradation efficiency is strongly influenced by PFAS molecular structure, with fluorotelomer sulfonates (FTS) and [[Wikipedia: Perfluorobutanesulfonic acid | perfluorobutanesulfonate (PFBS)]] exhibiting greater resistance to degradation by UV/sulfite treatment compared to other PFAS compounds.
  
The first pilot study with the PFASigator<small><sup>TM</sup></small> was conducted in late 2023 at an industrial facility in Michigan with PFAS-impacted groundwater. The goal of the pilot study was to treat the groundwater to below the limits for regulatory discharge permits. For the pilot demonstration, the PFASigator<small><sup>TM</sup></small> was paired with an FF unit, which pre-concentrated the PFAS into a foamate that was pumped into the PFASigator<small><sup>TM</sup></small> for batch PFAS destruction. Residual PFAS remaining after the destruction batch was treated by looping back the PFASigator<small><sup>TM</sup></small> effluent to the FF system influent. During the one-month field pilot duration, site-specific discharge limits were met, and steady state operation between the FF unit and PFASigator<small><sup>TM</sup></small> was achieved such that the PFASigator<small><sup>TM</sup></small> destroyed the required concentrated PFAS mass and no off-site disposal of PFAS contaminated waste was required.
+
==State of the Practice==
 +
[[File: XiongFig2.png | thumb | 500 px | Figure 2. Field demonstration of EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/> for PFAS destruction in a concentrated waste stream in a Mid-Atlantic Naval Air Station: a) Target PFAS at each step of the treatment shows that about 99% of PFAS were destroyed; meanwhile, the final degradation product, i.e., fluoride, increased to 15 mg/L in concentration, demonstrating effective PFAS destruction; b) AOF concentrations at each step of the treatment provided additional evidence to show near-complete mineralization of PFAS. Average results from multiple batches of treatment are shown here.]]
 +
[[File: XiongFig3.png | thumb | 500 px | Figure 3. Field demonstration of a treatment train (SAFF + EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/>) for groundwater PFAS separation and destruction at an Air Force base in California: a) Two main components of the treatment train, i.e. SAFF and EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/>; b) Results showed the effective destruction of various PFAS in the foam fractionate. The target PFAS at each step of the treatment shows that about 99.9% of PFAS were destroyed. Meanwhile, the final degradation product, i.e., fluoride, increased to 30 mg/L in concentration, demonstrating effective destruction of PFAS in a foam fractionate concentrate. After a polishing treatment step (GAC) via the onsite groundwater extraction and treatment system, all PFAS were removed to concentrations below their MCLs.]] 
 +
The effectiveness of UV/sulfite technology for treating PFAS has been evaluated in two field demonstrations using the EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/> system. Aqueous samples collected from the system were analyzed using EPA Method 1633, the [[Wikipedia: TOP Assay | total oxidizable precursor (TOP) assay]], adsorbable organic fluorine (AOF) method, and non-target analysis. A summary of each demonstration and their corresponding PFAS treatment efficiency is provided below.
 +
*Under the [https://serdp-estcp.mil/ Environmental Security Technology Certification Program (ESTCP)] [https://serdp-estcp.mil/projects/details/4c073623-e73e-4f07-a36d-e35c7acc75b6/er21-5152-project-overview Project ER21-5152], a field demonstration of EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/> was conducted at a Navy site on the east coast, and results showed that the technology was highly effective in destroying various PFAS in a liquid concentrate produced from an ''in situ'' foam fractionation groundwater treatment system. As shown in Figure 2a, total PFAS concentrations were reduced from 17,366 micrograms per liter (µg/L) to 195 µg/L at the end of the UV/sulfite reaction, representing 99% destruction. After the ion exchange resin polishing step, all residual PFAS had been removed to the non-detect level, except one compound (PFOS) reported as 1.5 nanograms per liter (ng/L), which is below the current Maximum Contaminant Level (MCL) of 4 ng/L. Meanwhile, the fluoride concentration increased up to 15 milligrams per liter (mg/L), confirming near complete defluorination. Figure 2b shows the adsorbable organic fluorine results from the same treatment test, which similarly demonstrates destruction of 99% of PFAS.
 +
*Another field demonstration was completed at an Air Force base in California, where a treatment train combining [https://serdp-estcp.mil/projects/details/263f9b50-8665-4ecc-81bd-d96b74445ca2 Surface Active Foam Fractionation (SAFF)] and EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/> was used to treat PFAS in groundwater. As shown in Figure 3, PFAS analytical data and fluoride results demonstrated near-complete destruction of various PFAS. In addition, this demonstration showed: a) high PFAS destruction ratio was achieved in the foam fractionate, even in very high concentration (up to 1,700 mg/L of booster), and b) the effluent from EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/> was sent back to the influent of the SAFF system for further concentration and treatment, resulting in a closed-loop treatment system and no waste discharge from EradiFluor<sup><small>TM</small></sup><ref name="EradiFluor"/>. This field demonstration was conducted with the approval of three regulatory agencies (United States Environmental Protection Agency, California Regional Water Quality Control Board, and California Department of Toxic Substances Control).
  
 
==References==
 
==References==

Latest revision as of 11:33, 29 January 2026

PFAS Destruction by Ultraviolet/Sulfite Treatment

The ultraviolet (UV)/sulfite based reductive defluorination process has emerged as an effective and practical option for generating hydrated electrons (eaq- ) which can destroy PFAS in water. It offers significant advantages for PFAS destruction, including significant defluorination, high treatment efficiency for long-, short-, and ultra-short chain PFAS without mass transfer limitations, selective reactivity by hydrated electrons, low energy consumption, low capital and operation costs, and no production of harmful byproducts. A UV/sulfite treatment system designed and developed by Haley and Aldrich (EradiFluorTM[1]) has been demonstrated in two field demonstrations in which it achieved near-complete defluorination and greater than 99% destruction of 40 PFAS analytes measured by EPA method 1633.

Related Article(s):

Contributors: John Xiong, Yida Fang, Raul Tenorio, Isobel Li, and Jinyong Liu

Key Resources:

  • Defluorination of Per- and Polyfluoroalkyl Substances (PFAS) with Hydrated Electrons: Structural Dependence and Implications to PFAS Remediation and Management[2]
  • Accelerated Degradation of Perfluorosulfonates and Perfluorocarboxylates by UV/Sulfite + Iodide: Reaction Mechanisms and System Efficiencies[3]
  • Destruction of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous Film-Forming Foam (AFFF) with UV-Sulfite Photoreductive Treatment[4]
  • EradiFluorTM[1]

Introduction

The hydrated electron (eaq- ) can be described as an electron in solution surrounded by a small number of water molecules[5]. Hydrated electrons can be produced by photoirradiation of solutes, including sulfite, iodide, dithionite, and ferrocyanide, and have been reported in literature to effectively decompose per- and polyfluoroalkyl substances (PFAS) in water. The hydrated electron is one of the most reactive reducing species, with a standard reduction potential of about −2.9 volts. Though short-lived, hydrated electrons react rapidly with many species having more positive reduction potentials[5].

Among the electron source chemicals, sulfite (SO32−) has emerged as one of the most effective and practical options for generating hydrated electrons to destroy PFAS in water. The mechanism of hydrated electron production in a sulfite solution under ultraviolet is shown in Equation 1 (UV is denoted as hv, SO3•- is the sulfur trioxide radical anion):

Equation 1:   XiongEq1.png

The hydrated electron has demonstrated excellent performance in destroying PFAS such as perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA)[6] and GenX[7]. Mechanisms include cleaving carbon-to-fluorine (C-F) bonds (i.e., hydrogen/fluorine atom exchange) and chain shortening (i.e., decarboxylation, hydroxylation, elimination, and hydrolysis)[2].

Process Description

A commercial UV/sulfite treatment system designed and developed by Haley and Aldrich (EradiFluorTM[1]) includes an optional pre-oxidation step to transform PFAS precursors (when present) and a main treatment step to break C-F bonds by UV/sulfite reduction. The effluent from the treatment process can be sent back to the influent of a pre-treatment separation system (such as a foam fractionation, regenerable ion exchange, or a membrane filtration system) for further concentration or sent for off-site disposal in accordance with relevant disposal regulations. A conceptual treatment process diagram is shown in Figure 1.

Figure 1: Conceptual Treatment Process for a Concentrated PFAS Stream


Advantages

A UV/sulfite treatment system offers significant advantages for PFAS destruction compared to other technologies, including high defluorination percentage, high treatment efficiency for short-chain PFAS without mass transfer limitation, selective reactivity by eaq-, low energy consumption, and the production of no harmful byproducts. A summary of these advantages is provided below:

  • High efficiency for short- and ultrashort-chain PFAS: While the degradation efficiency for short-chain PFAS is challenging for some treatment technologies[8][9][10], the UV/sulfite process demonstrates excellent defluorination efficiency for both short- and ultrashort-chain PFAS, including trifluoroacetic acid (TFA) and perfluoropropionic acid (PFPrA).
  • High defluorination ratio: As shown in Figure 3, the UV/sulfite treatment system has demonstrated near 100% defluorination for various PFAS under both laboratory and field conditions.
  • No harmful byproducts: While some oxidative technologies, such as electrochemical oxidation, generate toxic byproducts, including perchlorate, bromate, and chlorate, the UV/sulfite system employs a reductive mechanism and does not generate these byproducts.
  • Ambient pressure and low temperature: The system operates under ambient pressure and low temperature (<60°C), as it utilizes UV light and common chemicals to degrade PFAS.
  • Low energy consumption: The electrical energy per order values for the degradation of perfluorocarboxylic acids (PFCAs) by UV/sulfite have been reduced to less than 1.5 kilowatt-hours (kWh) per cubic meter under laboratory conditions. The energy consumption is orders of magnitude lower than that for many other destructive PFAS treatment technologies (e.g., supercritical water oxidation)[11].
  • Co-contaminant destruction: The UV/sulfite system has also been reported effective in destroying certain co-contaminants in wastewater. For example, UV/sulfite is reported to be effective in reductive dechlorination of chlorinated volatile organic compounds, such as trichloroethene, 1,2-dichloroethane, and vinyl chloride[12][13][14][15].

Limitations

Several environmental factors and potential issues have been identified that may impact the performance of the UV/sulfite treatment system, as listed below. Solutions to address these issues are also proposed.

  • Environmental factors, such as the presence of elevated concentrations of natural organic matter (NOM), dissolved oxygen, or nitrate, can inhibit the efficacy of UV/sulfite treatment systems by scavenging available hydrated electrons. Those interferences are commonly managed through chemical additions, reaction optimization, and/or dilution, and are therefore not considered likely to hinder treatment success.
  • Coloration in waste streams may also impact the effectiveness of the UV/sulfite treatment system by blocking the transmission of UV light, thus reducing the UV lamp's effective path length. To address this, pre-treatment may be necessary to enable UV/sulfite destruction of PFAS in the waste stream. Pre-treatment may include the use of strong oxidants or coagulants to consume or remove UV-absorbing constituents.
  • The degradation efficiency is strongly influenced by PFAS molecular structure, with fluorotelomer sulfonates (FTS) and perfluorobutanesulfonate (PFBS) exhibiting greater resistance to degradation by UV/sulfite treatment compared to other PFAS compounds.

State of the Practice

Figure 2. Field demonstration of EradiFluorTM[1] for PFAS destruction in a concentrated waste stream in a Mid-Atlantic Naval Air Station: a) Target PFAS at each step of the treatment shows that about 99% of PFAS were destroyed; meanwhile, the final degradation product, i.e., fluoride, increased to 15 mg/L in concentration, demonstrating effective PFAS destruction; b) AOF concentrations at each step of the treatment provided additional evidence to show near-complete mineralization of PFAS. Average results from multiple batches of treatment are shown here.
Figure 3. Field demonstration of a treatment train (SAFF + EradiFluorTM[1]) for groundwater PFAS separation and destruction at an Air Force base in California: a) Two main components of the treatment train, i.e. SAFF and EradiFluorTM[1]; b) Results showed the effective destruction of various PFAS in the foam fractionate. The target PFAS at each step of the treatment shows that about 99.9% of PFAS were destroyed. Meanwhile, the final degradation product, i.e., fluoride, increased to 30 mg/L in concentration, demonstrating effective destruction of PFAS in a foam fractionate concentrate. After a polishing treatment step (GAC) via the onsite groundwater extraction and treatment system, all PFAS were removed to concentrations below their MCLs.

The effectiveness of UV/sulfite technology for treating PFAS has been evaluated in two field demonstrations using the EradiFluorTM[1] system. Aqueous samples collected from the system were analyzed using EPA Method 1633, the total oxidizable precursor (TOP) assay, adsorbable organic fluorine (AOF) method, and non-target analysis. A summary of each demonstration and their corresponding PFAS treatment efficiency is provided below.

  • Under the Environmental Security Technology Certification Program (ESTCP) Project ER21-5152, a field demonstration of EradiFluorTM[1] was conducted at a Navy site on the east coast, and results showed that the technology was highly effective in destroying various PFAS in a liquid concentrate produced from an in situ foam fractionation groundwater treatment system. As shown in Figure 2a, total PFAS concentrations were reduced from 17,366 micrograms per liter (µg/L) to 195 µg/L at the end of the UV/sulfite reaction, representing 99% destruction. After the ion exchange resin polishing step, all residual PFAS had been removed to the non-detect level, except one compound (PFOS) reported as 1.5 nanograms per liter (ng/L), which is below the current Maximum Contaminant Level (MCL) of 4 ng/L. Meanwhile, the fluoride concentration increased up to 15 milligrams per liter (mg/L), confirming near complete defluorination. Figure 2b shows the adsorbable organic fluorine results from the same treatment test, which similarly demonstrates destruction of 99% of PFAS.
  • Another field demonstration was completed at an Air Force base in California, where a treatment train combining Surface Active Foam Fractionation (SAFF) and EradiFluorTM[1] was used to treat PFAS in groundwater. As shown in Figure 3, PFAS analytical data and fluoride results demonstrated near-complete destruction of various PFAS. In addition, this demonstration showed: a) high PFAS destruction ratio was achieved in the foam fractionate, even in very high concentration (up to 1,700 mg/L of booster), and b) the effluent from EradiFluorTM[1] was sent back to the influent of the SAFF system for further concentration and treatment, resulting in a closed-loop treatment system and no waste discharge from EradiFluorTM[1]. This field demonstration was conducted with the approval of three regulatory agencies (United States Environmental Protection Agency, California Regional Water Quality Control Board, and California Department of Toxic Substances Control).

References

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See Also