Difference between revisions of "User:Jhurley/sandbox"

From Enviro Wiki
Jump to: navigation, search
(→‎Application of Plasma for the Treatment of PFAS-Contaminated Water)
(→‎State of the Practice)
 
(910 intermediate revisions by the same user not shown)
Line 1: Line 1:
−
==PFAS Treatment by Electrical Discharge Plasma==
+
==PFAS Destruction by Ultraviolet/Sulfite Treatment==  
−
Plasma-based water treatment is a technology that, using only electricity, converts water into a mixture of highly reactive species including OH•, O, H•, HO<sub>2</sub>•, O<sub>2</sub>•<sup>‒</sup>, H<sub>2</sub>, O<sub>2</sub>, H<sub>2</sub>O<sub>2</sub> and aqueous electrons (e<sup>‒</sup><sub>aq</sub>), called a plasma<ref name="Sunka1999">Sunka, P., Babický, V., Clupek, M., Lukes, P., Simek, M., Schmidt, J., and Cernak, M., 1999. Generation of Chemically Active Species by Electrical Discharges in Water. Plasma Sources Science and Technology, 8(2), pp. 258-265. [https://doi.org/10.1088/0963-0252/8/2/006 DOI: 10.1088/0963-0252/8/2/006]</ref><ref name="MededovicThagard2009">Mededovic Thagard, S., Takashima, K., and Mizuno, A., 2009. Chemistry of the Positive and Negative Electrical Discharges Formed in Liquid Water and Above a Gas-Liquid Surface. Plasma Chemistry and Plasma Processing, 29(6), pp.455-473. [https://doi.org/10.1007/s11090-009-9195-x DOI: 10.1007/s11090-009-9195-x]</ref>. These highly reactive species rapidly and non-selectively degrade [[Wikipedia: Volatile organic compound |volatile organic compounds (VOCs)]]<ref name="Du2019">Du, C., Gong, X., and Lin, Y., 2019. Decomposition of volatile organic compounds using corona discharge plasma technology. Journal of the Air and Waste Management Association, 69(8), pp.879-899.  [https://doi.org/10.1080/10962247.2019.1582441 DOI: 10.1080/10962247.2019.1582441]  [https://www.tandfonline.com/doi/full/10.1080/10962247.2019.1582441 Open access article.]</ref>, [[1,4-Dioxane | 1,4-dioxane]]<ref name="Xiong2019">Xiong, Y., Zhang, Q., Wandell, R., Bresch, S., Wang, H., Locke, B.R. and Tang, Y., 2019. Synergistic 1,4-Dioxane Removal by Non-Thermal Plasma Followed by Biodegradation. Chemical Engineering Journal, 361, pp.519-527. [https://doi.org/10.1016/J.CEJ.2018.12.094 DOI: 10.1016/J.CEJ.2018.12.094]</ref><ref name="Ni2013">Ni, G.H., Zhao, Y., Meng, Y.D., Wang, X.K., and Toyoda, H., 2013. Steam plasma jet for treatment of contaminated water with high-concentration 1,4-dioxane organic pollutants. Europhysics Letters, 101(4), p.45001. [https://doi.org/10.1209/0295-5075/101/45001 DOI: 10.1209/0295-5075/101/45001]</ref>, and a broad spectrum of [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | per- and polyfluoroalkyl substances (PFAS)]] including perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and short-chain PFAS<ref name="Stratton2015">Stratton, G.R., Bellona, C.L., Dai, F., Holsen, T.M. and Mededovic Thagard, S., 2015. Plasma-Based Water Treatment: Conception and Application of a New General Principle for Reactor Design. Chemical Engineering Journal, 273, pp.543-550. [https://doi.org/10.1016/j.cej.2015.03.059 DOI: 10.1016/j.cej.2015.03.059]</ref><ref name="Singh2019a">Singh, R.K., Multari, N., Nau-Hix, C., Anderson, R.H., Richardson, S.D., Holsen, T.M. and Mededovic Thagard, S., 2019. Rapid Removal of Poly- and Perfluorinated Compounds from Investigation-Derived Waste (IDW) in a Pilot-Scale Plasma Reactor. Environmental Science and Technology, 53(19), pp.11375-11382. [https://doi.org/10.1021/acs.est.9b02964 DOI: 10.1021/acs.est.9b02964]</ref><ref name="Singh2019b">Singh, R.K., Fernando, S., Baygi, S.F., Multari, N., Mededovic Thagard, S., and Holsen, T.M., 2019. Breakdown Products from Perfluorinated Alkyl Substances (PFAS) Degradation in a Plasma-Based Water Treatment Process. Environmental Science and Technology, 53(5), pp.2731-2738. [https://doi.org/10.1021/acs.est.8b07031 DOI: 10.1021/acs.est.8b07031]</ref>. A plasma reactor can simultaneously oxidize and reduce organics by producing a mixture of hydroxyl radicals and aqueous electrons, the latter of which act as strong reducing agents and could be the key species in removing PFAS and other non-oxidizable compounds. Additionally, the plasma process produces no residual waste and requires no chemical additions, although adding surfactants or injecting inert gas into the liquid phase can increase interfacial PFAS concentrations, exposing more of the PFAS to the plasma and therefore increasing removal efficiency.  
+
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 Ex Situ Water Treatment]]
 
*[[PFAS Ex Situ Water Treatment]]
 +
*[[PFAS Sources]]
 +
*[[PFAS Treatment by Electrical Discharge Plasma]]
 +
*[[Supercritical Water Oxidation (SCWO)]]
 +
*[[Photoactivated Reductive Defluorination - PFAS Destruction]]
  
−
'''Contributor(s):'''  
+
'''Contributors:''' John Xiong, Yida Fang, Raul Tenorio, Isobel Li, and Jinyong Liu
−
*Dr. Selma Mededovic Thagard
 
−
*Dr. Thomas Holsen
 
−
*Dr. Stephen Richardson, P.E
 
−
*Poonam Kulkarni, P.E.
 
−
*Dr. Blossom Nzeribe
 
  
−
'''Key Resource(s):'''
+
'''Key Resources:'''
−
* [https://pfas-1.itrcweb.org/12-treatment-technologies/#12_2  PFAS – Per- and Polyfluoroalkyl Substances: 12.2 Field-Implemented Liquids Treatment Technologies. Interstate Technology Regulatory Council (ITRC).]  See also: [https://pfas-1.itrcweb.org/12-treatment-technologies/#12_5 12.5 Limited Application and Developing Liquids Treatment Technologies].
+
*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>
−
 
+
*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>
−
* Physico-Chemical Processes for the Treatment of Per- And Polyfluoroalkyl Substances (PFAS): A review28<ref name="Nzeribe2019">Nzeribe, B.N., Crimi, M., Mededovic Thagard, S. and 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>
+
*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"/>
−
* Low Temperature Plasma for Biology, Hygiene, and Medicine: Perspective and Roadmap<ref name="Laroussi2021">Laroussi, M., Bekeschus, S., Keidar, M., Bogaerts, A., Fridman, A., Lu, X.P., Ostrikov, K.K., Hori, M., Stapelmann, K., Miller, V., Reuter, S., Laux, C., Mesbah, A., Walsh, J., Jiang, C., Mededovic Thagard, S., Tanaka, H., Liu, D.W., Yan, D., and Yusupov, M., 2021. Low Temperature Plasma for Biology, Hygiene, and Medicine: Perspective and Roadmap. IEEE Transactions on Radiation and Plasma Medical Sciences. [https://doi.org/10.1109/TRPMS.2021.3135118 DOI: 10.1109/TRPMS.2021.3135118] [https://ieeexplore.ieee.org/abstract/document/9650590 Open access article.]</ref>
 
  
 
==Introduction==
 
==Introduction==
−
[[File:Plasma4PFASFig1.png | thumb |left|700px|Figure 1. Plasmas generated within liquids (Courtesy of Plasma Research Laboratory, Clarkson University)]]
+
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"/>.  
−
Plasma processing plays an essential role in various industrial applications such as semiconductor fabrication, polymer functionalization, chemical synthesis, agriculture and food safety, health industry, and hazardous waste management<ref name="VanVeldhuizen2002">Van Veldhuizen, E.M., and Rutgers, W.R., 2002. Pulsed Positive Corona Streamer Propagation and Branching. Journal of Physics D: Applied Physics, 35(17), p.2169.  [https://doi.org/10.1088/0022-3727/35/17/313 DOI: 10.1088/0022-3727/35/17/313]</ref><ref name="Yang">Yang, Y., Cho, Y.I. and Fridman, A., 2012. Plasma Discharge in Liquid: Water Treatment and Applications. CRC press. ISBN: 978-1-4398-6623-8  [https://doi.org/10.1201/b11650 DOI: 10.1201/b11650]</ref><ref name="Rezaei2019">Rezaei, F., Vanraes, P., Nikiforov, A., Morent, R., and De Geyter, N., 2019. Applications of Plasma-Liquid Systems: A Review. Materials, 12(17), article 2751, 69 pp.  [https://doi.org/10.3390/ma12172751 DOI: 10.3390/ma12172751]&nbsp;&nbsp;  [https://www.mdpi.com/1996-1944/12/17/2751 Open access article].</ref><ref name="Herianto2021">Herianto, S., Hou, C.Y., Lin, C.M., and Chen, H.L., 2021. Nonthermal plasma-activated water: A comprehensive review of this new tool for enhanced food safety and quality. Comprehensive Reviews in Food Science and Food Safety, 20(1), pp. 583-626. [https://doi.org/10.1111/1541-4337.12667 DOI: 10.1111/1541-4337.12667]</ref>.  Plasma is a gaseous state of matter consisting of charged particles, metastable-state molecules or atoms, and free radicals. Depending on the energy or temperature of the electrons, compared with the temperature of the background gas, plasmas can be classified as thermal or non-thermal. In thermal plasma, an example of which is an electrical arc, individual species’ temperatures typically exceed several thousand kelvins (K). Non-thermal plasmas are formed using less power with temperatures ranging from ambient to approximately 1000 K<ref name="Jiang2014">Jiang, B., Zheng, J., Qiu, S., Wu, M., Zhang, Q., Yan, Z. and Xue, Q., 2014. Review on Electrical Discharge Plasma Technology for Wastewater Remediation. Chemical Engineering Journal, 236, pp. 348–368. [https://doi.org/10.1016/j.cej.2013.09.090 DOI: 10.1016/j.cej.2013.09.090]</ref>. An example of a non-thermal plasma is a dielectric barrier discharge used for commercial ozone generation.
 
−
 
 
−
Plasma that is applied in water treatment (Figure 1) is typically non-thermal, which offers high-energy process efficiency and selectivity<ref name="Jiang2014"/><ref name="Magureanu2018">Magureanu, M., Bradu, C., and Parvulescu, V.I., 2018. Plasma Processes for the Treatment of Water Contaminated with Harmful Organic Compounds. Journal of Physics D: Applied Physics, 51(31), p. 313002. [https://doi.org/10.1088/1361-6463/aacd9c DOI:    10.1088/1361-6463/aacd9c]</ref>. Since the 1980s when the first plasma reactor was utilized to oxidize a dye<ref name="Clements1987">Clements, J.S., Sato, M., and Davis, R.H., 1987. Preliminary Investigation of Prebreakdown Phenomena and Chemical Reactions Using a Pulsed High-Voltage Discharge in Water. IEEE Transactions on Industry Applications, IA-23(2), pp. 224-235. [https://doi.org/10.1109/TIA.1987.4504897 DOI: 10.1109/TIA.1987.4504897]</ref>, over a hundred different plasma reactors have been developed to treat a range of contaminants of environmental importance including biological species. Examples include treatment of pharmaceuticals, volatile organic compounds (VOCs), 1,4-dioxane, herbicides, pesticides, warfare agents, bacteria, yeasts and viruses using direct-in-liquid discharges with and without bubbles and discharges in a gas over and contacting the surface of a liquid. Different excitation sources including AC, nanosecond pulsed and DC voltages have been utilized to produce pulsed corona, corona-like, spark, arc, and glow discharges, among other discharge types. Many reviews of plasma processing for water treatment applications have recently been published<ref name="Zeghioud2020">Zeghioud, H., Nguyen-Tri, P., Khezami, L., Amrane, A., and Assadi, A.A., 2020. Review on Discharge Plasma for Water Treatment: Mechanism, Reactor Geometries, Active Species and Combined Processes. Journal of Water Process Engineering, 38, p.101664. [https://doi.org/10.1016/j.jwpe.2020.101664 DOI: 10.1016/j.jwpe.2020.101664]</ref><ref name="Murugesan2020">Murugesan, P., Evanjalin Monica, V., Moses, J.A., and Anandharamakrishnan, C., 2020. Water Decontamination Using Non-Thermal Plasma: Concepts, Applications, and Prospects. Journal of Environmental Chemical Engineering, 8(5), p. 104377. [https://doi.org/10.1016/j.jece.2020.104377 DOI: 10.1016/j.jece.2020.104377]</ref>.
 
−
[[File: Plasma4PFASFig2.png | thumb |500px|Figure 2. Continuous flow enhanced contact plasma treatment system (Courtesy of Plasma Research Laboratory, Clarkson University).]]
 
−
Plasma-based water treatment (PWT) owes its strong oxidation and disinfection capabilities to the production of reactive oxidative species (ROS), primarily OH radicals, atomic oxygen, singlet oxygen and hydrogen peroxide. The process also produces reductive species such as solvated electrons and reactive nitrogen species (RNS) when nitrogen and oxygen are present in the discharge. This process has the advantage of synergistic effects of high electric fields, UV/VUV light emissions and in some cases shockwave formation in a liquid. It requires no chemical additions, and can be optimized for batch or continuous processing.
 
−
 
 
−
==Application of Plasma for the Treatment of PFAS-Contaminated Water==
 
−
Several research groups have investigated the use of plasma to treat and remove PFAS from contaminated water<ref name="Hayashi2015">Hayashi, R., Obo, H., Takeuchi, N., and Yasuoka, K., 2015. Decomposition of Perfluorinated Compounds in Water by DC Plasma within Oxygen Bubbles. Electrical Engineering in Japan, 190(3), pp.9-16. [https://doi.org/10.1002/eej.22499 DOI: 10.1002/eej.22499]&nbsp;&nbsp;  [https://onlinelibrary.wiley.com/doi/full/10.1002/eej.22499 Open access article].</ref><ref name="Matsuya2014">Matsuya, Y., Takeuchi, N., Yasuoka, K., 2014. Relationship Between Reaction Rate of Perfluorocarboxylic Acid Decomposition at a Plasma-Liquid Interface and Adsorbed Amount. Electrical Engineering in Japan, 188(2), pp.1-8. [https://doi.org/10.1002/eej.22526 DOI:  10.1002/eej.22526]&nbsp;&nbsp; [https://onlinelibrary.wiley.com/doi/full/10.1002/eej.22526 Open access article].</ref><ref name="Stratton2017">Stratton, G.R., Dai, F., Bellona, C.L., Holsen, T.M., Dickenson, E.R., and Mededovic Thagard, S., 2017. Plasma-Based Water Treatment: Efficient Transformation of Perfluoroalkyl Substances in Prepared Solutions and Contaminated Groundwater. Environmental Science and Technology, 51(3), pp.1643-1648. [https://doi.org/10.1021/acs.est.6b04215 DOI: 10.1021/acs.est.6b04215]</ref><ref name="Takeuchi2013">Takeuchi, N., Kitagawa, Y., Kosugi, A., Tachibana, K., Obo, H., and Yasuoka, K., 2013. Plasma-Liquid Interfacial Reaction in Decomposition of Perfluoro Surfactants. Journal of Physics D: Applied Physics, 47(4), p.045203. [https://doi.org/10.1088/0022-3727/47/4/045203 DOI: 10.1088/0022-3727/47/4/045203]</ref><ref name="Yasuoka2011">Yasuoka, K., Sasaki, K., and Hayashi, R., 2011. An Energy-Efficient Process for Decomposing Perfluorooctanoic and Perfluorooctane Sulfonic Acids Using DC Plasmas Generated within Gas Bubbles. Plasma Sources Science and Technology, 20(3), p. 034009. [https://doi.org/10.1088/0963-0252/20/3/034009 DOI: 10.1088/0963-0252/20/3/034009]</ref><ref name="Yasuoka2010">Yasuoka, K., Sasaki, K., Hayashi, R., Kosugi, A., and Takeuchi, N., 2010. Degradation of Perfluoro Compounds and F<sup>-</sup> Recovery in Water Using Discharge Plasmas Generated within Gas Bubbles. International Journal of Plasma Environmental Science and Technology, 4(2), 113–117.  [http://ijpest.com/Contents/04/2/PDF/04-02-113.pdf Open access article].</ref><ref name="Lewis2020">Lewis, A.J., Joyce, T., Hadaya, M., Ebrahimi, F., Dragiev, I., Giardetti, N., Yang, J., Fridman, G., Rabinovich, A., Fridman, A.A., McKenzie, E.R., and Sales, C.M., 2020. Rapid Degradation of PFAS in Aqueous Solutions by Reverse Vortex Flow Gliding Arc Plasma. Environmental Science: Water Research and Technology, 6(4), pp.1044-1057. [https://doi.org/10.1039/c9ew01050e DOI: 10.1039/c9ew01050e]</ref><ref name="Saleem2020">Saleem, M., Biondo, O., Sretenović, G., Tomei, G., Magarotto, M., Pavarin, D., Marotta, E. and Paradisi, C., 2020. Comparative Performance Assessment of Plasma Reactors for the Treatment of PFOA; Reactor Design, Kinetics, Mineralization and Energy Yield. Chemical Engineering Journal, 382, p.123031. [https://doi.org/10.1016/j.cej.2019.123031 DOI: 10.1016/j.cej.2019.123031]</ref><ref name="Palma2021">Palma, D., Papagiannaki, D., Lai, M., Binetti, R., Sleiman, M., Minella, M. and Richard, C., 2021. PFAS Degradation in Ultrapure and Groundwater Using Non-Thermal Plasma. Molecules, 26(4), p. 924. [https://doi.org/10.3390/molecules26040924 DOI: 10.3390/molecules26040924]&nbsp;&nbsp; [https://www.mdpi.com/1420-3049/26/4/924/htm Open access article].</ref>.  Of those studies, the Enhanced Contact (EC) plasma reactor developed by researchers at Clarkson University is one of the most promising in terms of treatment time, cost, the range of PFAS treated and scale up/throughput. Their process has been shown to degrade PFOA, PFOS, and other PFAS in a variety of PFAS-impacted water sources.  
 
  
−
[[File: Plasma4PFASFig3.png | thumb |left|350px|Figure 3. Degradation profiles of combined PFOA and PFOS concentrations in investigation derived waste (IDW) obtained from nine different Air Force site investigations. In all the IDW samples, both PFOS and PFOA were removed to below EPA’s lifetime health advisory level concentrations (70 ng/L) in < 1 minute of treatment, demonstrating the lack of sensitivity of the plasma-based process to the effects of co-contaminants<ref name="Singh2019a"/>.]]
+
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):
−
[[File: Plasma4PFASFig4.png | thumb |600px|Figure 4. (a) Mobile plasma treatment trailer depicting the (b) plasma side of the trailer featuring two plasma reactors and the plasma-generating network; and (c) control and plumbing side of the plasma trailer featuring multiple rotameters, storage tanks and plumbing.]]
+
</br>
−
In the EC plasma reactor (Figure 2), argon gas is continuously pumped through the solution to form a layer of foam and thus concentrate PFAS at the gas-liquid interface where plasma is formed. The process is able to lower the concentrations of PFOA and PFOS in groundwater obtained from multiple DoD sites to below Environmental Protection Agency’s (EPA’s) lifetime health advisory level (HAL) of 70 parts per trillion (70 nanogram per liter, ng/L)<ref name="USEPA2016">US Environmental Protection Agency (EPA), 2016. Lifetime Health Advisories and Health Effects Support Documents for Perfluorooctanoic Acid and Perfluorooctane Sulfonate. Federal Register, Notices, 81(101), p. 33250-33251.  [https://www.epa.gov/sites/production/files/2016-05/documents/2016-12361.pdf Free download].</ref> within 1 minute of treatment (Figure 3) with energy requirements much lower than those of alternative technologies (~2-6 kWh/m3 for plasma vs. 5000 kWh/m3 for persulfate, photochemical oxidation and sonolytic processes and 132 kWh/m3 for electrochemical oxidation)<ref name="Singh2019a"/><ref name="Nzeribe2019"/>. The EC plasma reactor owes its high efficacy to the plasma reactor design, in particular to the gas bubbling through submerged diffusers to transport PFAS to the plasma-liquid interface and thus minimize bulk liquid limitations.
+
::<big>'''Equation 1:'''</big>&nbsp;&nbsp; [[File: XiongEq1.png | 200 px]]
−
[[File: Plasma4PFASFig5.png | thumb |left|350px|Figure 5. Plasma destruction of PFAS-impacted groundwater at the fire-training area at Wright-Patterson Air Force Base<ref name="Nau-Hix2021"/>. One cycle = 18 gallons.]]
 
−
In 2019, a mobile plasma treatment system (Figure 4) was successfully demonstrated for the treatment of PFAS-contaminated groundwater at the fire-training area at Wright-Patterson Air Force Base<ref name="Nau-Hix2021">Nau-Hix, C., Multari, N., Singh, R.K., Richardson, S., Kulkarni, P., Anderson, R.H., Holsen, T.M. and Mededovic Thagard, S., 2021. Field Demonstration of a Pilot-Scale Plasma Reactor for the Rapid Removal of Poly-and Perfluoroalkyl Substances in Groundwater. ACS ES&T Water, 1(3), pp. 680-687. [https://doi.org/10.1021/acsestwater.0c00170 DOI: 10.1021/acsestwater.0c00170]</ref>.
 
  
−
Over 300 gallons of PFAS-impacted groundwater were treated at a maximum flowrate of 1.1  gallon per minute (gpm) resulting in ≥90% reduction (mean percent removal of 99.7%) of long-chain PFAAs (fluorocarbon chain ≥ 6) and PFAS precursors in a single pass through the reactor (Figure 5) at a treatment cost of $7.30/1000 gallons<ref name="Nau-Hix2021"/>. As expected, the removal of short-chain PFAS was slower due to their lower potential for interfacial adsorption compared to long-chain PFAS. However, post-field laboratory studies revealed that the addition of a cationic surfactant such as CTAB (cetrimonium bromide) minimizes bulk liquid transport limitations for short-chain PFAS by electrostatically interacting with these compounds and transporting them to the plasma-liquid interface where they are degraded.26 Both bench and pilot-scale EC plasma-based process have been extended for the treatment of PFAS in membrane concentrate, ion exchange brine, and landfill leachate<ref name="Singh2020">Singh, R.K., Multari, N., Nau-Hix, C., Woodard, S., Nickelsen, M., Mededovic Thagard, S. and Holsen, 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.13973-13980. [https://doi.org/10.1021/acs.est.0c02158 DOI: 10.1021/acs.est.0c02158]</ref><ref name="Singh2021">Singh, R.K., Brown, E., Mededovic Thagard, S., and Holsen, T.M., 2021. Treatment of PFAS-Containing Landfill Leachate Using an Enhanced Contact Plasma Reactor. Journal of Hazardous Materials, 408, p.124452. [https://doi.org/10.1016/j.jhazmat.2020.124452 DOI: 10.1016/j.jhazmat.2020.124452]</ref>.  
+
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"/>.
  
−
As a part of a currently-funded ESTCP project (ESTCP ER20-5535)<ref name="Mededovic2020">Mededovic, S., 2020. An Innovative Plasma Technology for Treatment of AFFF Rinsate from Firefighting Delivery Systems. Environmental Security Technology Certification Program (ESTCP), Project ER20-5355. [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/ER20-5355  Project Overview]</ref>, the Clarkson University team with the support of GSI Environmental Inc. is evaluating the effectiveness of their plasma process in treating diluted aqueous film-forming foams (AFFFs) as well as the benefits of pre-oxidation of PFAS precursors in high concentration AFFF solutions in terms of post-oxidation plasma treatment time, destruction efficiency and cost.
+
==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"/>
  
−
==Advantages and Limitations of the Technology for PFAS Treatment==
+
==Advantages==
−
===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 removal rates of long-chain PFAS (C5-C8) due to the production of versatile reactive species
+
*'''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)]]. 
−
* Requires no chemical additions and produces no residual waste
+
*'''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.
−
* Total organic carbon (TOC) concentration and other non-surfactant co-contaminants do not influence the process efficiency
+
*'''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.
−
* The process is mobile and scalable
+
*'''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. 
−
* Versatile: can be used in batch and continuous systems
+
*'''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>.
  
−
===Limitations:===
+
==Limitations==
−
* Removal of short-chain PFAS due to their inability to concentrate at plasma-liquid interfaces. Addition of surfactants such as CTAB improves their removal and degradation rates.
+
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.
−
* Excessive foaming caused by bubbling argon gas through a solution containing high (>10 mg/L) concentrations of long-chain (surfactant) PFAS may interfere with the formation of plasma.
+
*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.
  
−
==Summary==
+
==State of the Practice==
−
PFAS are susceptible to plasma treatment because the hydrophobic PFAS accumulates at the gas-liquid interface, exposing more of the PFAS to the plasma. Plasma-based treatment of PFAS contaminated water successfully degrades PFOA and PFOS to below the EPA health advisory level of 70 ppt and accomplishes the near complete destruction of other PFAS within a short treatment time. PFAS concentration reductions of ≥90% and post-treatment concentrations below laboratory detection levels are common for long chain PFAS and precursors.   
+
[[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 lack of sensitivity of plasma to co-contaminants, coupled with high PFAS removal and defluorination efficiencies, makes plasma-based water treatment a promising technology for the remediation of PFAS-contaminated water. The plasma treatment process is currently developed for ex situ application and can also be integrated into a treatment train<ref name="Richardson2021">Richardson, S., 2021. Nanofiltration Followed by Electrical Discharge Plasma for Destruction of PFAS and Co-occurring Chemicals in Groundwater: A Treatment Train Approach. Environmental Security Technology Certification Program (ESTCP), Project Number ER21-5136. [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/ER21-5136  Project Overview]</ref>.
+
[[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

  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"