Difference between revisions of "User:Jhurley/sandbox"

From Enviro Wiki
Jump to: navigation, search
(→‎Industrial Sources)
(→‎State of the Practice)
 
Line 1: Line 1:
−
==PFAS Sources==
+
==PFAS Destruction by Ultraviolet/Sulfite Treatment==  
−
[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] have been used in coatings for textiles, paper products, and cookware; in some firefighting foams; and have a range of applications in the aerospace, photographic imaging, semiconductor, automotive, construction, electronics, and aviation industries<ref name="ITRC2020">Interstate Technology and Regulatory Council (ITRC), 2020. Technical/Regulatory Guidance: Per- and Polyfluoroalkyl Substances (PFAS), PFAS-1. ITRC, PFAS Team, Washington DC. Website:  https://pfas-1.itrcweb.org/ &nbsp;&nbsp; [https://pfas-1.itrcweb.org/wp-content/uploads/2020/04/ITRC_PFAS_TechReg_April2020.pdf  Free Download from ITRC].&nbsp;&nbsp; [[Media: ITRC_PFAS-1.pdf | Report.pdf]]</ref><ref name="KEMI2015">Swedish Chemicals Agency (KEMI), 2015. Occurrence and use of highly fluorinated substances and alternatives, Report 7/15. ISSN 0284-1185. Article number 361 164.  [[Media: KEMI2015.pdf | Report.pdf]]</ref><ref name="USEPA2021">US Environmental Protection Agency (USEPA), 2021. Basic Information on PFAS. [https://www.epa.gov/pfas/basic-information-pfas#tab-1 Website]</ref>. Although PFAS and PFAS-containing products have been manufactured since the 1950s, PFAS were not widely documented in environmental samples until the early 2000s. Understanding PFAS manufacturing history, past and current uses, and waste management over the last six to seven decades is necessary for the identification of potential environmental sources of PFAS, possible release mechanisms, and associated pathway-receptor relationships.
+
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.
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
  
 
'''Related Article(s):'''
 
'''Related Article(s):'''
  
−
* [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
+
*[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
−
* [[PFAS Transport and Fate]]
+
*[[PFAS Ex Situ Water Treatment]]
 +
*[[PFAS Sources]]
 +
*[[PFAS Treatment by Electrical Discharge Plasma]]
 +
*[[Supercritical Water Oxidation (SCWO)]]
 +
*[[Photoactivated Reductive Defluorination - PFAS Destruction]]
  
−
'''Contributor(s):''' [[Dr. Sheau-Yun (Dora) Chiang]] and [[Dr. Alexandra Salter-Blanc]]
+
'''Contributors:''' John Xiong, Yida Fang, Raul Tenorio, Isobel Li, and Jinyong Liu
  
−
'''Key Resource(s):'''
+
'''Key Resources:'''
−
 
+
*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>
−
*[https://pfas-1.itrcweb.org/wp-content/uploads/2020/04/ITRC_PFAS_TechReg_April2020.pdf Per- and Polyfluoroalkyl Substances (PFAS), PFAS-1. ITRC 2020.]<ref name="ITRC2020"/>
+
*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>
 +
*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>
 +
*EradiFluor<sup>TM</sup><ref name="EradiFluor"/>
  
 
==Introduction==
 
==Introduction==
−
[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] are a complex family of more than 3,000 manmade fluorinated organic chemicals<ref name="Wang2017">Wang, Z., DeWitt, J.C., Higgins, C.P., and Cousins, I.T., 2017. A Never-Ending Story of Per- and Poly-Fluoroalkyl Substances (PFASs)? Environmental Science and Technology, 51(5), pp. 2508-2518.  [https://doi.org/10.1021/acs.est.6b04806 DOI: 10.1021/acs.est.6b04806]&nbsp;&nbsp; [[Media: Wang2017.pdf | Open access article.]]</ref> although not all of these are currently in use or production. PFAS are produced using several different processes. Fluorosurfactants, which include perfluoroalkyl acids (PFAAs) (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] article for nomenclature) and side-chain fluorinated polymers, have been manufactured using two major processes: [[Wikipedia: Electrochemical fluorination | electrochemical fluorination (ECF)]] and [[Wikipedia: Telomerization | telomerization]]<ref name="KEMI2015"/>. ECF was licensed by 3M in the 1940s<ref name="Banks1994">Banks, R.E., Smart, B.E. and Tatlow, J.C. eds., 1994. Organofluorine Chemistry: Principles and Commercial Applications. Springer Science and Business Media, New York, N. Y. [https://link.springer.com/book/10.1007/978-1-4899-1202-2 DOI: 10.1007/978-1-4899-1202-2]</ref> and used by 3M until 2001. ECF produces a mixture of even and odd numbered carbon chain lengths of approximately 70% linear and 30% branched substances<ref name="Concawe2016">Concawe (Conservation of Clean Air and Water in Europe), 2016.  Environmental fate and effects of poly- and perfluoroalkyl substances (PFAS).  Report No. 8/16. Brussels, Belgium. [[Media:Concawe2016.pdf | Report.pdf]]</ref>. Telomerization was developed in the 1970s<ref name="Benskin2012a">Benskin, J.P., Ahrens, L., Muir, D.C., Scott, B.F., Spencer, C., Rosenberg, B., Tomy, G., Kylin, H., Lohmann, R. and Martin, J.W., 2012. Manufacturing Origin of Perfluorooctanoate (PFOA) in Atlantic and Canadian Arctic Seawater. Environmental Science and Technology, 46(2), pp. 677-685.  [https://doi.org/10.1021/es202958p DOI: 10.1021/es202958p]</ref>, and yields mainly even numbered, straight carbon chain isomers<ref name="Kissa2001">Kissa, E., 2001. Fluorinated Surfactants and Repellents, Second Edition. Surfactant Science Series, Vol. 97. Marcel Dekker, Inc., CRC Press, New York. 640 pages. ISBN: 9780824704728</ref><ref name="Parsons2008">Parsons, J.R., Sáez, M., Dolfing, J. and De Voogt, P., 2008. Biodegradation of Perfluorinated Compounds. Reviews of Environmental Contamination and Toxicology, 196, pp. 53-71. Springer, New York, NY.  [https://doi.org/10.1007/978-0-387-78444-1_2 DOI: 10.1007/978-0-387-78444-1_2]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Jan_Dolfing/publication/23489065_Biodegradation_of_Perfluorinated_Compounds/links/0912f5087a40c9d5df000000.pdf ResearchGate]</ref>.  PFAS manufacturers have provided PFAS to secondary manufacturers for production of a vast array of industrial and consumer products.
+
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"/>.  
−
 
 
−
During manufacturing, PFAS may be released into the atmosphere then redeposited on land where they can also affect surface water and groundwater, or PFAS may be discharged without treatment to wastewater treatment plants or landfills, and eventually be released into the environment by treatment systems that are not designed to mitigate PFAS (see also [[PFAS Transport and Fate]]). Industrial discharges of PFAS were unregulated for many years, but that has begun to change. In January 2016, New York became the first state in the nation to regulate PFOA as a hazardous substance followed by the regulation of PFOS in April 2016. Consumer and industrial uses of PFAS-containing products can also end up releasing PFAS into landfills and into municipal wastewater, where it may accumulate undetected in biosolids which are typically treated by land application.
 
−
 
 
−
==Industrial Sources==
 
−
PFAS are used in many industrial and consumer applications, which may have released PFAS into the environment and impacted drinking water supplies in many areas of the United States<ref name="EWG2017">Environmental Working Group (EWG) and Northeastern University Social Science Environmental Health Research Institute, 2017. Mapping A Contamination Crisis. [https://www.ewg.org/research/mapping-contamination-crisis Website]</ref>. Both in the United States (US) and abroad, primary manufacturing facilities produce PFAS and secondary manufacturing facilities use PFAS to produce goods. Environmental release mechanisms associated with these facilities include air emission and dispersion, spills, and disposal of manufacturing wastes and wastewater. Potential impacts to air, soil, sediment, surface water, stormwater, and groundwater are present not only at primary release points but potentially over the surrounding area<ref name="Shin2011">Shin, H.M., Vieira, V.M., Ryan, P.B., Detwiler, R., Sanders, B., Steenland, K., and Bartell, S.M., 2011. Environmental Fate and Transport Modeling for Perfluorooctanoic Acid Emitted from the Washington Works Facility in West Virginia. Environmental Science and Technology, 45(4), pp. 1435-1442.  [https://doi.org/10.1021/es102769t DOI: 10.1021/es102769t]</ref>. Some of the potential primary and secondary sources of PFAS releases to the environment are listed here<ref name="ITRC2020"/>:
 
−
 
 
−
* '''Textiles and leather:''' Factory or consumer applied coating to repel water, oil, and stains. Applications include protective clothing and outerwear, umbrellas, tents, sails, architectural materials, carpets, and upholstery<ref name="Rao1994">Rao, N.S., and Baker, B.E., 1994. Textile Finishes and Fluorosurfactants. In: Organofluorine Chemistry, Banks, R.E., Smart, B.E., and Tatlow, J.C., Eds. Springer, New York.  [https://doi.org/10.1007/978-1-4899-1202-2_15 DOI: 10.1007/978-1-4899-1202-2_15]</ref><ref name="Hekster2003">Hekster, F.M., Laane, R.W. and De Voogt, P., 2003. Environmental and Toxicity Effects of Perfluoroalkylated Substances. Reviews of Environmental Contamination and Toxicology, 179, pp. 99-121. Springer, New York, NY. [https://doi.org/10.1007/0-387-21731-2_4 DOI: 10.1007/0-387-21731-2_4]</ref><ref name="Brooke2004">Brooke, D., Footitt, A., and Nwaogu, T.A., 2004. Environmental Risk Evaluation Report: Perfluorooctanesulphonate (PFOS).  Environment Agency (UK), Science Group.  Free download from: [http://chm.pops.int/Portals/0/docs/from_old_website/documents/meetings/poprc/submissions/Comments_2006/sia/pfos.uk.risk.eval.report.2004.pdf The Stockholm Convention]&nbsp;&nbsp; [[Media:Brooke2004.pdf | Report.pdf]]</ref><ref name="Poulsen2005">Poulsen, P.B., Jensen, A.A., and Wallström, E., 2005. More environmentally friendly alternatives to PFOS-compounds and PFOA. Danish Environmental Protection Agency, Environmental Project 1013.  [[Media: Poulsen2005.pdf | Report.pdf]]</ref><ref name="Prevedouros2006">Prevedouros, K., Cousins, I.T., Buck, R.C. and Korzeniowski, S.H., 2006. Sources, Fate and Transport of Perfluorocarboxylates. Environmental Science and Technology, 40(1), pp. 32-44.  [https://doi.org/10.1021/es0512475 DOI: 10.1021/es0512475]&nbsp;&nbsp; Free download from: [https://www.academia.edu/download/39945519/Sources_Fate_and_Transport_of_Perfluoroc20151112-1647-19vcvbf.pdf Academia.edu]</ref><ref name="Walters2006">Walters, A., and Santillo, D., 2006. Technical Note 06/2006: Uses of Perfluorinated Substances. Greenpeace Research Laboratories. [http://www.greenpeace.to/publications/uses-of-perfluorinated-chemicals.pdf Website]&nbsp;&nbsp; [[Media: Walters2006.pdf | Report.pdf]]</ref><ref name="Trudel2008">Trudel, D., Horowitz, L., Wormuth, M., Scheringer, M., Cousins, I.T. and Hungerbühler, K., 2008. Estimating Consumer Exposure to PFOS and PFOA. Risk Analysis: An International Journal, 28(2), pp. 251-269.  [https://doi.org/10.1111/j.1539-6924.2008.01017.x DOI: 10.1111/j.1539-6924.2008.01017.x]</ref><ref name="Guo2009">Guo, Z., Liu, X., Krebs, K.A. and Roache, N.F., 2009. Perfluorocarboxylic Acid Content in 116 Articles of Commerce, EPA/600/R-09/033. National Risk Management Research Laboratory, US Environmental Protection Agency, Washington, DC.  Available from: [https://cfpub.epa.gov/si/si_public_record_report.cfm?Lab=NRMRL&dirEntryId=206124 US EPA.]&nbsp;&nbsp; [[Media: Guo2009.pdf | Report.pdf]]</ref><ref name="USEPA2009">US Environmental Protection Agency (USEPA), 2009. Long-Chain Perfluorinated Chemicals (PFCs), Action Plan.  [https://www.epa.gov/sites/production/files/2016-01/documents/pfcs_action_plan1230_09.pdf Website]&nbsp;&nbsp; [[Media: USEPA2009.pdf | Report.pdf]]</ref><ref name="Ahrens2011a">Ahrens, L., 2011. Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate. Journal of Environmental Monitoring, 13(1), pp.20-31.
 
−
[http://dx.doi.org/10.1039/C0EM00373E DOI: 10.1039/C0EM00373E]. Free download available from: [https://www.researchgate.net/profile/Lutz_Ahrens/publication/47622154_Polyfluoroalkyl_compounds_in_the_aquatic_environment_A_review_of_their_occurrence_and_fate/links/00b7d53762cfedaf12000000/Polyfluoroalkyl-compounds-in-the-aquatic-environment-A-review-of-their-occurrence-and-fate.pdf ResearchGate]</ref><ref name="Buck2011">Buck, R.C., Franklin, J., Berger, U., Conder, J.M., Cousins, I.T., De Voogt, P., Jensen, A.A., Kannan, K., Mabury, S.A. and van Leeuwen, S.P., 2011. Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins. Integrated Environmental Assessment and Management, 7(4), pp. 513-541. [https://doi.org/10.1002/ieam.258 DOI: 10.1002/ieam.258]&nbsp;&nbsp; [[Media:Buck2011.pdf | Open access article.]]</ref><ref name="UNEP2011">United Nations Environmental Programme (UNEP), 2011. Report of the persistent organic pollutants review committee on the work of its sixth meeting, Addendum, Guidance on alternatives to perfluorooctane sulfonic acid and its derivatives, UNEP/POPS/POPRC.6/13/Add.3/Rev.1 [http://www.pops.int/TheConvention/POPsReviewCommittee/Meetings/POPRC6/POPRC6Documents/tabid/783/ctl/Download/mid/3507/Default.aspx?id=125 Website]&nbsp;&nbsp; [[Media: UNEP2011.pdf | Report.pdf]]</ref><ref name="Herzke2012">Herzke, D., Olsson, E. and Posner, S., 2012. Perfluoroalkyl and polyfluoroalkyl substances (PFASs) in consumer products in Norway – A pilot study. Chemosphere, 88(8), pp. 980-987.  [https://doi.org/10.1016/j.chemosphere.2012.03.035 DOI: 10.1016/j.chemosphere.2012.03.035]</ref><ref name="Patagonia2016">Patagonia, Inc., 2016. An Update on Our DWR Problem.  [https://www.patagonia.com/stories/our-dwr-problem-updated/story-17673.html Website]&nbsp;&nbsp; [[Media: Patagonia2016.pdf | Report.pdf]]</ref><ref name="Kotthoff2015">Kotthoff, M., Müller, J., Jürling, H., Schlummer, M., and Fiedler, D., 2015. Perfluoroalkyl and polyfluoroalkyl substances in consumer products. Environmental Science and Pollution Research, 22(19), pp. 14546-14559.  [https://doi.org/10.1007/s11356-015-4202-7 DOI: 10.1007/s11356-015-4202-7]&nbsp;&nbsp; [[Media: Kotthoff2015.pdf | Open access article.]]</ref><ref name="ATSDR2018">Agency for Toxic Substances and Disease Registry (ATSDR), 2018. Toxicological Profile for Perfluoroalkyls, Draft for Public Comment. US Department of Health and Human Services. Free download from: [http://www.atsdr.cdc.gov/toxprofiles/tp200.pdf ATSDR]&nbsp;&nbsp; [[Media: ATSDR2018.pdf | Report.pdf]]</ref>.
 
−
 
 
−
* '''Paper products:''' Surface coatings to repel grease and moisture. Uses include non-food paper packaging (for example, cardboard, carbonless forms, masking papers) and food-contact materials (for example, pizza boxes, fast food wrappers, microwave popcorn bags, baking papers, pet food bags)<ref name="Rao1994"/><ref name="Kissa2001"/><ref name="Hekster2003"/><ref name="Poulsen2005"/><ref name="Trudel2008"/><ref name="Buck2011"/><ref name="UNEP2011"/><ref name="Kotthoff2015"/><ref name="Schaider2017">Schaider, L.A., Balan, S.A., Blum, A., Andrews, D.Q., Strynar, M.J., Dickinson, M.E., Lunderberg, D.M., Lang, J.R., and Peaslee, G.F., 2017. Fluorinated Compounds in US Fast Food Packaging. Environmental Science and Technology Letters, 4(3), pp. 105-111.  [https://doi.org/10.1021/acs.estlett.6b00435 DOI: 10.1021/acs.estlett.6b00435]&nbsp;&nbsp; [[Media: Schaider2017.pdf | Open access article.]]</ref>
 
−
 
 
−
* '''Metal Plating & Etching:''' Corrosion prevention, mechanical wear reduction, aesthetic enhancement, surfactant, wetting agent/fume suppressant for chrome, copper, nickel and tin electroplating, and post-plating cleaner
 
−
 
 
−
 
 
−
 
 
−
 
 
  
 +
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):
 +
</br>
 +
::<big>'''Equation 1:'''</big>&nbsp;&nbsp; [[File: XiongEq1.png | 200 px]]
  
−
+
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"/>.
−
[[File:NewellMatrixDiffFig1.PNG | thumb |500px| Figure 1. Diffusion of a dissolved solute (chlorinated solvent) into lower ''K'' zones during loading period, followed by diffusion back out into higher ''K'' zones once the source is removed <ref name="Sale2007">Sale, T.C., Illangasekare, T.H., Zimbron, J., Rodriguez, D., Wilking, B., and Marinelli, F., 2007. AFCEE Source Zone Initiative. Air Force Center for Environmental Excellence, Brooks City-Base, San Antonio, TX. [https://www.enviro.wiki/images/0/08/AFCEE-2007-Sale.pdf Report.pdf]</ref>]]
 
  
 +
==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"/>
  
−
[[File: GreenTank.mp4 | thumb |500px| Figure 2. Video of dye tank simulation of matrix diffusion]]
+
==Advantages==
−
In some cases, matrix diffusion can maintain contaminant concentrations in more permeable zones above target cleanup goals for decades or potentially even centuries after the primary sources have been addressed.  At a site impacted by [[Wikipedia: Dense non-aqueous phase liquid | Dense Non-Aqueous Phase Liquids (DNAPL)]], [[Chlorinated Solvents | trichloroethene (TCE)]] concentrations in downgradient wells declined by roughly an order-of-magnitude (OoM) when the upgradient source area was isolated with sheet piling. However, after this initial decline, TCE concentrations appeared to plateau or decline more slowly, consistent with back diffusion from an underlying aquitard. Numerical simulations indicated that back diffusion would cause TCE concentrations in downgradient wells at the site to remain above target cleanup levels for centuries<ref name="Chapman2005"/>.  
+
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>.
  
−
One other implication of matrix diffusion is that plume migration is attenuated by the loss of contaminants into low permeability zones, leading to slower plume migration compared to a case where no matrix diffusion occurs. This phenomena was observed as far back as 1985 when Sudicky et al. observed that “A second consequence of the solute-storage effect offered by transverse diffusion into low-permeability layers is a rate of migration of the frontal portion of a contaminant in the permeable layers that is less than the groundwater velocity.”<ref name="Sudicky1985"> Sudicky, E.A., Gillham, R.W., and Frind, E.O., 1985. Experimental Investigation of Solute Transport in Stratified Porous Media: 1. The Nonreactive Case. Water Resources Research, 21(7), pp. 1035-1041. [https://doi.org/10.1029/WR021i007p01035 DOI: 10.1029/WR021i007p01035]</ref>  In cases where there is an attenuating source, matrix diffusion can also reduce the peak concentrations observed in downgradient monitoring wells. The attenuation caused by matrix diffusion may be particularly important for implementing [[Monitored Natural Attenuation (MNA)]] for contaminants that do not completely degrade, such as [[Metal and Metalloid Contaminants | heavy metals]] and [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]].
+
==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 [[Wikipedia: Perfluorobutanesulfonic acid | perfluorobutanesulfonate (PFBS)]] exhibiting greater resistance to degradation by UV/sulfite treatment compared to other PFAS compounds.
  
−
==SERPD/ESTCP Research==
+
==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.]]
−
The SERDP/ESTCP programs have funded several projects focusing on how matrix diffusion can impede progress towards reaching site closure, including:
+
[[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.
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-1740 SERDP Management of Contaminants Stored in Low Permeability Zones, A State-of-the-Science Review] <ref name="Sale2013"/>
+
*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).
−
|-
 
−
|
 
−
*[https://www.serdp-estcp.org/Tools-and-Training/Environmental-Restoration/Groundwater-Plume-Treatment/Matrix-Diffusion-Tool-Kit ESTCP Matrix Diffusion Toolkit]<ref name="Farhat2012">Farhat, S.K., Newell, C.J., Seyedabbasi, M.A., McDade, J.M., Mahler, N.T., Sale, T.C., Dandy, D.S. and Wahlberg, J.J., 2012. Matrix Diffusion Toolkit. Environmental Security Technology Certification Program (ESTCP) Project ER-201126.  [[Media:Farhat2012ER-201126UsersManual.pdf | User’s Manual.pdf]]  Website: [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201126 ER-201126]</ref>
 
−
|-
 
−
|
 
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-200530 ESTCP Decision Guide]<ref>Sale, T. and Newell, C., 2011. A Guide for Selecting Remedies for Subsurface Releases of Chlorinated Solvents. Environmental Security Technology Certification Program (ESTCP) Project ER-200530. [[Media: Sale2011ER-200530.pdf | Report.pdf]]  Website: [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-200530 ER-200530]</ref>
 
−
|-
 
−
|
 
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201426 ESTCP REMChlor-MD: the USEPA’s REMChlor model with a new matrix diffusion term for the plume]<ref name="Farhat2018">Farhat, S. K., Newell, C. J., Falta, R. W., and Lynch, K., 2018. A Practical Approach for Modeling Matrix Diffusion Effects in REMChlor. Environmental Security Technology Certification Program (ESTCP) Project ER-201426. [https://enviro.wiki/images/0/0b/2018-Falta-REMChlor_Modeling_Matrix_Diffusion_Effects.pdf  User’s Manual.pdf] Website: [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201426 ER-201426]</ref>
 
−
|}
 
−
[[File:ADRFig3.png | thumb| left |400px| Figure 3. Comparison of tracer breakthrough (upper graph) and cleanup curves (lower graph) from advection-dispersion based (gray lines) and advection-diffusion based (black lines) solute transport<ref name="ITRC2011">Interstate Technology and Regulatory Council (ITRC), 2011. Integrated DNAPL Site Strategy (IDSS-1),  Integrated DNAPL Site Strategy Team, ITRC, Washington, DC. [https://www.enviro.wiki/images/d/d9/ITRC-2011-Integrated_DNAPL.pdf Report.pdf]  Free download from: [https://itrcweb.org/GuidanceDocuments/IntegratedDNAPLStrategy_IDSSDoc/IDSS-1.pdf ITRC]</ref>.]]
 
−
 
 
−
==Transport Modeling==
 
−
Several different modeling approaches have been developed to simulate the diffusive transport of dissolved solutes into and out of lower ''K'' zones<ref>Falta, R.W., and Wang, W., 2017. A semi-analytical method for simulating matrix diffusion in numerical transport models. Journal of Contaminant Hydrology, 197, pp. 39-49.  [https://doi.org/10.1016/j.jconhyd.2016.12.007 DOI: 10.1016/j.jconhyd.2016.12.007]</ref><ref>Muskus, N. and Falta, R.W., 2018. Semi-analytical method for matrix diffusion in heterogeneous and fractured systems with parent-daughter reactions. Journal of Contaminant Hydrology, 218, pp. 94-109.  [https://doi.org/10.1016/j.jconhyd.2018.10.002 DOI: 10.1016/j.jconhyd.2018.10.002]</ref>.  The [https://www.serdp-estcp.org/Tools-and-Training/Environmental-Restoration/Groundwater-Plume-Treatment/Matrix-Diffusion-Tool-Kit Matrix Diffusion Toolkit]<ref name="Farhat2012"/> is a Microsoft Excel based tool for simulating forward and back diffusion using two different analytical models<ref name="Parker1994">Parker, B.L., Gillham, R.W., and Cherry, J.A., 1994. Diffusive Disappearance of Immiscible Phase Organic Liquids in Fractured Geologic Media. Groundwater, 32(5), pp. 805-820. [https://doi.org/10.1111/j.1745-6584.1994.tb00922.x DOI: 10.1111/j.1745-6584.1994.tb00922.x]</ref><ref>Sale, T.C., Zimbron, J.A., and Dandy, D.S., 2008. Effects of reduced contaminant loading on downgradient water quality in an idealized two-layer granular porous media. Journal of Contaminant Hydrology, 102(1), pp. 72-85. [https://doi.org/10.1016/j.jconhyd.2008.08.002 DOI: 10.1016/j.jconhyd.2008.08.002]</ref>.  Numerical models including [https://en.wikipedia.org/wiki/MODFLOW MODFLOW]/[https://xmswiki.com/wiki/GMS:MT3DMS MT3DMS]<ref name="Zheng1999">Zheng, C. and Wang, P.P., 1999. MT3DMS: A Modular Three-Dimensional Multispecies Transport Model for Simulation of Advection, Dispersion, and Chemical Reactions of Contaminants in Groundwater Systems; Documentation and User’s Guide. Contract Report SERDP-99-1 U.S. Army Engineer Research and Development Center, Vicksburg, MS. [https://www.enviro.wiki/images/3/32/Mt3dmanual.pdf User’s Guide.pdf]  [https://xmswiki.com/wiki/GMS:MT3DMS MT3DMS website]</ref> have been shown to be effective in simulating back diffusion processes and can accurately predict concentration changes over 3 orders-of-magnitude in heterogeneous sand tank experiments<ref>Chapman, S.W., Parker, B.L., Sale, T.C., Doner, L.A., 2012. Testing high resolution numerical models for analysis of contaminant storage and release from low permeability zones. Journal of Contaminant Hydrology, 136, pp. 106-116. [https://doi.org/10.1016/j.jconhyd.2012.04.006 DOI: 10.1016/j.jconhyd.2012.04.006]</ref>. However, numerical models require a fine vertical discretization with short time steps to accurately simulate back diffusion, greatly increasing computation times<ref>Farhat, S.K., Adamson, D.T., Gavaskar, A.R., Lee, S.A., Falta, R.W. and Newell, C.J., 2020. Vertical Discretization Impact in Numerical Modeling of Matrix Diffusion in Contaminated Groundwater. Groundwater Monitoring and Remediation, 40(2), pp. 52-64. [https://doi.org/10.1111/gwmr.12373 DOI: 10.1111/gwmr.12373]</ref>.  These issues can be addressed by incorporating a local 1-D model domain within a general 3D numerical model<ref>Carey, G.R., Chapman, S.W., Parker, B.L. and McGregor, R., 2015. Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes. Remediation, 25(4), pp. 55-79. [https://doi.org/10.1002/rem.21440 DOI: 10.1002/rem.21440]</ref>.
 
−
 
 
−
The [[REMChlor - MD]] toolkit is capable of simulating matrix diffusion in groundwater contaminant plumes by using a semi-analytical method for estimating mass transfer between high and low permeability zones that provides computationally accurate predictions, with much shorter run times than traditional fine grid numerical models<ref name="Farhat2018"/>.
 
−
 
 
−
==Impacts on Breakthrough Curves==
 
−
 
 
−
The impacts of matrix diffusion on the initial breakthrough of the solute plume and on later cleanup are illustrated in Figure 3<ref name="ITRC2011"/>. Using a traditional advection-dispersion model, the breakthrough curve for a pulse tracer injection appears as a bell-shaped ([[wikipedia:Gaussian function |Gaussian]]) curve (gray line on the right side of the upper graph) where the peak arrival time corresponds to the average groundwater velocity.  Using an advection-diffusion approach, the breakthrough curve for a pulse injection is asymmetric (solid black line) with the peak tracer concentration arriving earlier than would be expected based on the average groundwater velocity, but with a long extended tail to the flushout curve.
 
−
 
 
−
The lower graph shows the predicted cleanup concentration profiles following complete elimination of a source area.  The advection-dispersion model (gray line) predicts a clean-water front arriving at a time corresponding to the average groundwater velocity.  The advection-diffusion model (black line) predicts that concentrations will start to decline more rapidly than expected (based on the average groundwater velocity) as clean water rapidly migrates through the highest-permeability strata. However, low but significant contaminant concentrations linger much longer (tailing) due to diffusive contaminant mass exchange between zones of high and low permeability. A similar response to source remediation is seen in models such as the sand tank experiment shown in Figure 2, and also in field observations of plume contaminant concentrations in heterogeneous aquifers.
 
−
 
 
−
<br clear="left" />
 
  
 
==References==
 
==References==
−
 
 
<references />
 
<references />
  
 
==See Also==
 
==See Also==
−
 
−
*[http://www.gsi-net.com/en/publications/useful-groundwater-resources/colorado-state-matrix-diffusion-video.html Matrix Diffusion Movie]
 
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-1737 Impact of Clay-DNAPL Interactions on Transport and Storage of Chlorinated Solvents in Low Permeability Zones]
 
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-200320 Prediction of Groundwater Quality Improvement Down-Gradient of ''In Situ'' Permeable Treatment Barriers and Fully Remediated Source Zones]
 
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201032 Determining Source Attenuation History to Support Closure by Natural Attenuation]
 
−
*[https://www.coursera.org/learn/natural-attenuation-of-groundwater-contaminants/lecture/2R7yh/matrix-diffusion-principles Coursera Matrix Diffusion Online Lecture]
 

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

  1. ^ 1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 Haley and Aldrich, Inc. (commercial business), 2024. EradiFluor. Comercial Website
  2. ^ 2.0 2.1 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. doi: 10.1021/acs.est.8b06648  Open Access Article
  3. ^ 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. doi: 10.1021/acs.est.1c07608  Open Access Article
  4. ^ 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. doi: 10.1021/acs.est.0c00961
  5. ^ 5.0 5.1 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. doi: 10.1063/1.555805
  6. ^ 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. doi: 10.1016/j.scitotenv.2017.06.197
  7. ^ 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. doi: 10.1021/acs.est.8b02172
  8. ^ 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. doi: 10.1016/j.jhazmat.2020.124452
  9. ^ 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. doi: 10.1021/acs.est.0c02158
  10. ^ 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. doi: 10.1021/acsestwater.0c00170
  11. ^ 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. doi: 10.1080/10643389.2018.1542916
  12. ^ 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. doi: 10.1016/j.jece.2015.07.026
  13. ^ 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. doi: 10.1016/j.cej.2012.11.086
  14. ^ 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. doi: 10.1021/es3008535
  15. ^ 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. doi: 10.1016/j.watres.2014.05.051

See Also

Retrieved from "https://www.enviro.wiki/index.php?title=User:Jhurley/sandbox&oldid=17890"