|
|
| (463 intermediate revisions by the same user not shown) |
| Line 1: |
Line 1: |
| − | ==Photoactivated Reductive Defluorination PFAS Destruction== | + | ==Thermal Conduction Heating for Treatment of PFAS-Impacted Soil== |
| − | Photoactivated Reductive Defluorination (PRD) is a [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] destruction technology predicated on [[Wikipedia: Ultraviolet | ultraviolet (UV)]] light-activated photochemical reactions. The destruction efficiency of this process is enhanced by the use of a [[Wikipedia: Surfactant | surfactant]] to confine PFAS molecules in self-assembled [[Wikipedia: Micelle | micelles]]. The photochemical reaction produces [[Wikipedia: Solvated electron | hydrated electrons]] from an electron donor that associates with the micelle. The hydrated electrons have sufficient energy to rapidly cleave fluorine-carbon and other molecular bonds of PFAS molecules due to the association of the electron donor with the micelle. Micelle-accelerated PRD is a highly efficient method to destroy PFAS in a wide variety of water matrices.
| + | Removal of [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] compounds from impacted soils is challenging due to the modest volatility and varying properties of most PFAS compounds. Thermal treatment technologies have been developed for treatment of semi-volatile compounds in soils such as dioxins, furans, poly-aromatic hydrocarbons and poly-chlorinated biphenyls at temperatures near 325°C. In controlled bench-scale testing, complete removal of targeted PFAS compounds to concentrations below reporting limits of 0.5 µg/kg was demonstrated at temperatures of 400°C<ref name="CrownoverEtAl2019"> Crownover, E., Oberle, D., Heron, G., Kluger, M., 2019. Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation. Remediation Journal, 29(4), pp. 77-81. [https://doi.org/10.1002/rem.21623 doi: 10.1002/rem.21623]</ref>. Three field-scale thermal PFAS treatment projects that have been completed in the US include an in-pile treatment demonstration, an ''in situ'' vadose zone treatment demonstration and a larger scale treatment demonstration with excavated PFAS-impacted soil in a constructed pile. Based on the results, thermal treatment temperatures of at least 400°C and a holding time of 7-10 days are recommended for reaching local and federal PFAS soil standards. The energy requirement to treat typical wet soil ranges from 300 to 400 kWh per cubic yard, exclusive of heat losses which are scale dependent. Extracted vapors have been treated using condensation and granular activated charcoal filtration, with thermal and catalytic oxidation as another option which is currently being evaluated for field scale applications. Compared to other options such as soil washing, the ability to treat on site and to treat all soil fractions is an advantage. |
| | <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)]]
| |
| − | *[[PFAS Sources]]
| |
| − | *[[PFAS Transport and Fate]]
| |
| − | *[[PFAS Ex Situ Water Treatment]]
| |
| − | *[[Supercritical Water Oxidation (SCWO)]]
| |
| − | *[[PFAS Treatment by Electrical Discharge Plasma]]
| |
| | | | |
| − | '''Contributor(s):'''
| + | *[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] |
| − | *Dr. Suzanne Witt | + | *[[Thermal Conduction Heating (TCH)]] |
| − | *Dr. Meng Wang
| |
| − | *Dr. Denise Kay
| |
| | | | |
| − | '''Key Resource(s):''' | + | '''Contributors:''' Gorm Heron, Emily Crownover, Patrick Joyce, Ramona Iery |
| − | *Efficient Reductive Destruction of Perfluoroalkyl Substances under Self-Assembled Micelle Confinement<ref name="ChenEtAl2020">Chen, Z., Li, C., Gao, J., Dong, H., Chen, Y., Wu, B., Gu, C., 2020. Efficient Reductive Destruction of Perfluoroalkyl Substances under Self-Assembled Micelle Confinement. Environmental Science and Technology, 54(8), pp. 5178–5185. [https://doi.org/10.1021/acs.est.9b06599 doi: 10.1021/acs.est.9b06599]</ref>
| + | |
| − | *Complete Defluorination of Perfluorinated Compounds by Hydrated Electrons Generated from 3-Indole-Acetic-Acid in Organomodified Montmorillonite<ref name="TianEtAl2016">Tian, H., Gao, J., Li, H., Boyd, S.A., Gu, C., 2016. Complete Defluorination of Perfluorinated Compounds by Hydrated Electrons Generated from 3-Indole-Acetic-Acid in Organomodified Montmorillonite. Scientific Reports, 6(1), Article 32949. [https://doi.org/10.1038/srep32949 doi: 10.1038/srep32949] [[Media: TianEtAl2016.pdf | Open Access Article]]</ref>
| + | '''Key Resource:''' |
| − | *Application of Surfactant Modified Montmorillonite with Different Conformation for Photo-Treatment of Perfluorooctanoic Acid by Hydrated Electrons<ref name="ChenEtAl2019">Chen, Z., Tian, H., Li, H., Li, J. S., Hong, R., Sheng, F., Wang, C., Gu, C., 2019. Application of Surfactant Modified Montmorillonite with Different Conformation for Photo-Treatment of Perfluorooctanoic Acid by Hydrated Electrons. Chemosphere, 235, pp. 1180–1188. [https://doi.org/10.1016/j.chemosphere.2019.07.032 doi: 10.1016/j.chemosphere.2019.07.032]</ref>
| + | *Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation<ref name="CrownoverEtAl2019"/> |
| − | *[https://serdp-estcp.mil/projects/details/c4e21fa2-c7e2-4699-83a9-3427dd484a1a ER21-7569: Photoactivated Reductive Defluorination PFAS Destruction]<ref name="WittEtAl2023">Kay, D., Witt, S., Wang, M., 2023. Photoactivated Reductive Defluorination PFAS Destruction: Final Report. ESTCP Project ER21-7569. [https://serdp-estcp.mil/projects/details/c4e21fa2-c7e2-4699-83a9-3427dd484a1a Project Website] [[Media: ER21-7569_Final_Report.pdf | Final Report.pdf]]</ref> | |
| | | | |
| | ==Introduction== | | ==Introduction== |
| − | [[File:WittFig1.png | thumb |400px|Figure 1. Schematic of PRD mechanism<ref name="WittEtAl2023"/>]] | + | [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] have become prominent emerging contaminants in soil and groundwater. Soil source zones have been identified at locations where the chemicals were produced, handled or used. Few effective options exist for treatments that can meet local and federal soil standards. Over the past 30 plus years, thermal remediation technologies have grown from experimental and innovative prospects to mature and accepted solutions deployed effectively at many sites. More than 600 thermal case studies have been summarized by Horst and colleagues<ref name="HorstEtAl2021">Horst, J., Munholland, J., Hegele, P., Klemmer, M., Gattenby, J., 2021. In Situ Thermal Remediation for Source Areas: Technology Advances and a Review of the Market From 1988–2020. Groundwater Monitoring & Remediation, 41(1), p. 17. [https://doi.org/10.1111/gwmr.12424 doi: 10.1111/gwmr.12424] [[Media: gwmr.12424.pdf | Open Access Manuscript]]</ref>. [[Thermal Conduction Heating (TCH)]] has been used for higher temperature applications such as removal of [[1,4-Dioxane]]. This article reports recent experience with TCH treatment of PFAS-impacted soil. |
| − | The Photoactivated Reductive Defluorination (PRD) process is based on a patented chemical reaction that breaks fluorine-carbon bonds and disassembles PFAS molecules in a linear fashion beginning with the [[Wikipedia: Hydrophile | hydrophilic]] functional groups and proceeding through shorter molecules to complete mineralization. Figure 1 shows how PRD is facilitated by adding [[Wikipedia: Cetrimonium bromide | cetyltrimethylammonium bromide (CTAB)]] to form a surfactant micelle cage that traps PFAS. A non-toxic proprietary chemical is added to solution to associate with the micelle surface and produce hydrated electrons via stimulation with UV light. These highly reactive hydrated electrons have the energy required to cleave fluorine-carbon and other molecular bonds resulting in the final products of fluoride, water, and simple carbon molecules (e.g., formic acid and acetic acid). The methods, mechanisms, theory, and reactions described herein have been published in peer reviewed literature<ref name="ChenEtAl2020"/><ref name="TianEtAl2016"/><ref name="ChenEtAl2019"/><ref name="WittEtAl2023"/>.
| |
| | | | |
| − | ==Advantages and Disadvantages== | + | ==Target Temperature and Duration== |
| − | </br>
| + | PFAS behave differently from most other organics subjected to TCH treatment. While the boiling points of individual PFAS fall in the range of 150-400°C, their chemical and physical behavior creates additional challenges. Some PFAS form ionic species in certain pH ranges and salts under other chemical conditions. This intricate behavior and our limited understanding of what this means for our ability to remove the PFAS from soils means that direct testing of thermal treatment options is warranted. Crownover and colleagues<ref name="CrownoverEtAl2019"/> subjected PFAS-laden soil to bench-scale heating to temperatures between 200 and 400°C which showed strong reductions of PFAS concentrations at 350°C and complete removal of many PFAS compounds at 400°C. The soil concentrations of targeted PFAS were reduced to nearly undetectable levels in this study. |
| − | {|
| |
| − | | || '''Equation 1:'''
| |
| − | | [[File: Equation1r.png]]
| |
| − | |-
| |
| − | | Where: || ||
| |
| − | |-
| |
| − | | || ''C<sub>0</sub>''|| is the freely dissolved concentration of the analyte in the sediment (mg/L or μg/L)
| |
| − | |-
| |
| − | | || ''C<sub>p,t</sub>'' || is the measured concentration of the analyte in the peeper at time of retrieval (mg/L or μg/L)
| |
| − | |-
| |
| − | | || ''K'' || is the elimination rate of the target analyte
| |
| − | |-
| |
| − | | || ''t'' || is the deployment time (days)
| |
| − | |}
| |
| | | | |
| − | </br>
| + | ==Heating Method== |
| − | {|
| + | For semi-volatile compounds such as dioxins, furans, poly-chlorinated biphenyls (PCBs) and Poly-Aromatic Hydrocarbons (PAH), thermal conduction heating has evolved as the dominant thermal technology because it is capable of achieving soil temperatures higher than the boiling point of water, which are necessary for complete removal of these organic compounds. Temperatures between 200 and 500°C have been required to achieve the desired reduction in contaminant concentrations<ref name="StegemeierVinegar2001">Stegemeier, G.L., Vinegar, H.J., 2001. Thermal Conduction Heating for In-Situ Thermal Desorption of Soils. Ch. 4.6, pp. 1-37. In: Chang H. Oh (ed.), Hazardous and Radioactive Waste Treatment Technologies Handbook, CRC Press, Boca Raton, FL. ISBN 9780849395864 [[Media: StegemeierVinegar2001.pdf | Open Access Article]]</ref>. TCH has become a popular technology for PFAS treatment because temperatures in the 400°C range are needed. |
| − | | || '''Equation 2:'''
| |
| − | | [[File: Equation2r.png]]
| |
| − | |-
| |
| − | | Where: || ||
| |
| − | |-
| |
| − | | || ''K''|| is the elimination rate of the target analyte
| |
| − | |-
| |
| − | | || ''K<sub>tracer</sub>'' || is the elimination rate of the tracer
| |
| − | |-
| |
| − | | || ''D'' || is the free-water diffusion of the analyte (cm<sup>2</sup>/s)
| |
| − | |- | |
| − | | || ''D<sub>tracer</sub>'' || is the free-water diffusion of the tracer (cm<sup>2</sup>/s)
| |
| − | |}
| |
| | | | |
| − | </br>
| + | The energy source for TCH can be electricity (most commonly used), or fossil fuels (typically gas, diesel or fuel oil). Electrically powered TCH offers the largest flexibility for power input which also can be supplied by renewable and sustainable energy sources. |
| − | {|
| |
| − | | || '''Equation 3:'''
| |
| − | | [[File: Equation3r2.png]]
| |
| − | |-
| |
| − | | Where: || ||
| |
| − | |-
| |
| − | | || ''K<sub>tracer</sub>'' || is the elimination rate of the tracer
| |
| − | |-
| |
| − | | || ''C<sub>tracer,i</sub>''|| is the measured initial concentration of the tracer in the peeper prior to deployment (mg/L or μg/L)
| |
| − | |-
| |
| − | | || ''C<sub>tracer,t</sub>'' || is the measured final concentration of the tracer in the peeper at time of retrieval (mg/L or μg/L)
| |
| − | |-
| |
| − | | || ''t'' || is the deployment time (days)
| |
| − | |}
| |
| | | | |
| − | The self-assembly of [[Wikipedia: Amphiphile | amphiphilic]] molecules into supramolecular bilayers is a result of their structure and how it interacts with the bulk water of a solution. Single chain hydrocarbon based amphiphiles can form [[Wikipedia: Micelle | micelles]] under relatively dilute aqueous concentrations, however for hydrocarbon based surfactants the formation of more complex organized system such as [[Wikipedia: Vesicle (biology and chemistry) | vesicles]] is rarely seen, requiring double chain amphiphiles such as [[wikipedia: Phospholipid|phospholipids]]. Associations of single chain [[wikipedia: Ion#Anions_and_cations|cationic and anionic]] hydrocarbon based amphiphiles into stable supramolecular structures such as vesicles has however been demonstrated<ref>Fukuda, H., Kawata, K., Okuda, H., 1990. Bilayer-Forming Ion-Pair Amphiphiles from Single-Chain Surfactants. Journal of the American Chemical Society, 112(4), pp. 1635-1637. [https://doi.org/10.1021/ja00160a057 doi: 10.1021/ja00160a057]</ref>, with the ion pairing of the polar head groups mimicking the a double tail situation. The behavior of single chain [[wikipedia: Per-_and_polyfluoroalkyl_substances#Fluorosurfactants|fluorosurfactant]] amphiphiles has been demonstrated to be significantly different from similar hydrocarbon based analogues. Not only are [[Wikipedia: Critical micelle concentration | critical micelle concentrations (CMC)]] of fluorosurfactants typically two orders of magnitude lower than corresponding hydrocarbon surfactants but self-assembly can occur even when fluorosurfactants are dispersed at low concentrations significantly below the CMC in water and other solvents<ref name="Krafft2006">Krafft, M.P., 2006. Highly fluorinated compounds induce phase separation in, and nanostructuration of liquid media. Possible impact on, and use in chemical reactivity control. Journal of Polymer Science Part A: Polymer Chemistry, 44(14), pp. 4251-4258. [https://doi.org/10.1002/pola.21508 doi: 10.1002/pola.21508] [[Media:Krafft2006.pdf | Open Access Article]]</ref>. The assembly of fluorinated amphiphiles structurally similar to those found in AFFF have been shown to readily form stable, complex structures including vesicles, fibers, and globules at concentrations as low as 0.5% w/v in contrast to their hydrocarbon analogues which remained fluid at 30% w/v<ref>Krafft, M.P., Guilieri, F., Riess, J.G., 1993. Can Single-Chain Perfluoroalkylated Amphiphiles Alone form Vesicles and Other Organized Supramolecular Systems? Angewandte Chemie International Edition in English, 32(5), pp. 741-743. [https://doi.org/10.1002/anie.199307411 doi: 10.1002/anie.199307411]</ref><ref name="KrafftEtAl_1994">Krafft, M.P., Guilieri, F., Riess, J.G., 1994. Supramolecular assemblies from single chain perfluoroalkylated phosphorylated amphiphiles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 84(1), pp. 113-119. [https://doi.org/10.1016/0927-7757(93)02681-4 doi: 10.1016/0927-7757(93)02681-4]</ref>.
| + | ==Energy Usage== |
| | + | Treating PFAS-impacted soil with heat requires energy to first bring the soil and porewater to the boiling point of water, then to evaporate the porewater until the soil is dry, and finally to heat the dry soil up to the target treatment temperature. The energy demand for wet soils falls in the 300-400 kWh/cy range, dependent on porosity and water saturation. Additional energy is consumed as heat is lost to the surroundings and by vapor treatment equipment, yielding a typical usage of 400-600 kWh/cy total for larger soil treatment volumes. Wetter soils and small treatment volumes drive the energy usage towards the higher number, whereas larger soil volumes and dry soil can be treated with less energy. |
| | | | |
| − | Krafft found that fluorinated amphiphiles formed bilayer membranes with phospholipids, and that the resulting vesicles were more stable than those made of phospholipids alone<ref name="KrafftEtAl_1998">Krafft, M.P., Riess, J.G., 1998. Highly Fluorinated Amphiphiles and Collodial Systems, and their Applications in the Biomedical Field. A Contribution. Biochimie, 80(5-6), pp. 489-514. [https://doi.org/10.1016/S0300-9084(00)80016-4 doi: 10.1016/S0300-9084(00)80016-4]</ref>. The similarities in amphiphilic properties between phospholipids and the hydrocarbon-based surfactants in AFFF suggests that bilayer vesicles may form between these and the fluorosurfactants also present in the concentrate. Krafft demonstrated that both the permeability of resulting mixed vesicles and their propensity to fuse with each other at increasing ionic strength was reduced as a result of the creation of an inert hydrophobic and [[wikipedia: Lipophobicity|lipophobic]] film within the membrane, and also suggested that the fluorinated amphiphiles increased [[Wikipedia: van der Waals force | van der Waals interactions]] in the hydrocarbon region<ref name="KrafftEtAl_1998"/>. Thus this low permeability may allow vesicles formed by the surfactants present in AFFF to act as long term repositories of PFAS not only as part of the bilayer itself but also solvated within the vesicle. This prediction is supported by the observation that supramolecular structures formed from single chain fluorinated amphiphiles have been demonstrated to be stable at elevated temperature (15 min at 121°C) and have been shown to be stable over periods of months, even increasing in size over time when stored at environmentally relevant temperatures<ref name="KrafftEtAl_1994"/>.
| + | ==Vapor Treatment== |
| | + | During the TCH process a significant fraction of the PFAS compounds are volatilized by the heat and then removed from the soil by vacuum extraction. The vapors must be treated and eventually discharged while meeting local and/or federal standards. Two types of vapor treatment have been used in past TCH applications for organics: (1) thermal and catalytic oxidation and (2) condensation followed by granular activated charcoal (GAC) filtration. Due to uncertainties related to thermal destruction of fluorinated compounds and future requirements for treatment temperature and residence time, condensation and GAC filtration have been used in the first three PFAS treatment field demonstrations. It should be noted that PFAS compounds will stick to surfaces and that decontamination of the equipment is important. This could generate additional waste as GAC vessels, pipes and other wetted equipment need careful cleaning with solvents or rinsing agents such as PerfluorAd<sup><small>TM</small></sup>. |
| | | | |
| − | Formation of complex structures at relatively low solute concentrations requires the monomer molecules to be well ordered to maintain tight packing in the supramolecular structure<ref>Ringsdorf, H., Schlarb, B., Venzmer, J., 1988. Molecular Architecture and Function of Polymeric Oriented Systems: Models for the Study of Organization, Surface Recognition, and Dynamics of Biomembranes. Angewandte Chemie International Edition in English, 27(1), pp. 113-158. [https://doi.org/10.1002/anie.198801131 doi: 10.1002/anie.198801131]</ref>. This order results from electrostatic forces, [[wikipedia: Hydrogen bond|hydrogen bonding]], and in the case of fluorinated amphiphiles, hydrophobic interactions. The geometry of the amphiphile also potentially contributes to the type of supramolecular aggregation<ref>Israelachvili, J.N., Mitchell, D.J., Ninham, B.W., 1976. Theory of Self-Assembly of Hydrocarbon Amphiphiles into Micelles and Bilayers. Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics, 72, pp. 1525-1568. [https://doi.org/10.1039/F29767201525 doi: 10.1039/F29767201525]</ref>. Surfactants which adopt a conical shape (such as a typical hydrocarbon based surfactant with a large polar head group and a single alkyl chain as a tail) tend to form micelles more easily. Increasing the bulk of the tail makes the surfactant more cylindrically shaped which makes assembly into bilayers more likely.
| + | ==PFAS Reactivity and Fate== |
| | + | While evaluating initial soil treatment results, Crownover ''et al''<ref name="CrownoverEtAl2019"/> noted the lack of complete data sets when the soils were analyzed for non-targeted compounds or extractable precursors. Attempts to establish the fluorine balance suggest that the final fate of the fluorine in the PFAS is not yet fully understood. Transformations are likely occurring in the heated soil as demonstrated in laboratory experiments with and without calcium hydroxide (Ca(OH)<small><sub>2</sub></small>) amendment<ref>Koster van Groos, P.G., 2021. Small-Scale Thermal Treatment of Investigation-Derived Wastes Containing PFAS. [https://serdp-estcp.mil/ Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP)], [https://serdp-estcp.mil/projects/details/2f1577ac-c8ea-4ae8-804e-c9f97a12edb3/small-scale-thermal-treatment-of-investigation-derived-wastes-idw-containing-pfas Project ER18-1556 Website], [[Media: ER18-1556_Final_Report.pdf | Final Report.pdf]]</ref>. Amendments such as Ca(OH)<sub><small>2</small></sub> may be useful in reducing the required treatment temperature by catalyzing PFAS degradation. With thousands of PFAS potentially present, the interactions are complex and may never be fully understood. Therefore, successful thermal treatment may require a higher target temperature than for other organics with similar boiling points – simply to provide a buffer against the uncertainty. |
| | | | |
| − | Perfluoroalkyl chains are significantly more bulky than their hydrocarbon based analogues both in cross sectional area (28-30 Å<sup>2</sup> versus 20 Å<sup>2</sup>, respectively) and mean volume (CF<sub>2</sub> and CF<sub>3</sub> estimated as 38 Å<sup>3</sup> and 92 Å<sup>3</sup> compared to 27 Å<sup>3</sup> and 54 Å<sup>3</sup> for CH<sub>2</sub> and CH<sub>3</sub>)<ref name="KrafftEtAl_1998"/><ref name="Krafft2006"/>. Structural studies on linear PFOS have shown that the molecule adopts an unusual helical structure<ref>Erkoç, Ş., Erkoç, F., 2001. Structural and electronic properties of PFOS and LiPFOS. Journal of Molecular Structure: THEOCHEM, 549(3), pp. 289-293. [https://doi.org/10.1016/S0166-1280(01)00553-X doi:10.1016/S0166-1280(01)00553-X]</ref><ref name="TorresEtAl2009">Torres, F.J., Ochoa-Herrera, V., Blowers, P., Sierra-Alvarez, R., 2009. Ab initio study of the structural, electronic, and thermodynamic properties of linear perfluorooctane sulfonate (PFOS) and its branched isomers. Chemosphere 76(8), pp. 1143-1149. [https://doi.org/10.1016/j.chemosphere.2009.04.009 doi: 10.1016/j.chemosphere.2009.04.009]</ref> in aqueous and solvent phases to alleviate [[wikipedia: Steric_effects#Steric_hindrance|steric hindrance]]. This arrangement results from the carbon chain starting in the planar all anti [[wikipedia:Conformational isomerism|conformation]] and then successively twisting all the CC-CC dihedrals by 15°-20° in the same direction<ref>Abbandonato, G., Catalano, D., Marini, A., 2010. Aggregation of Perfluoroctanoate Salts Studied by <sup>19</sup>F NMR and DFT Calculations: Counterion Complexation, Poly(ethylene glycol) Addition, and Conformational Effects. Langmuir 26(22), pp. 16762-16770. [https://doi.org/10.1021/la102578k doi: 10.1021/la102578k].</ref>. The conformation also minimizes the electrostatic repulsion between fluorine atoms bonded to the same side of the carbon backbone by maximizing the interatomic distances between them<ref name="TorresEtAl2009"/>.
| + | ==Case Studies== |
| | + | ===Stockpile Treatment, Eielson AFB, Alaska ([https://serdp-estcp.mil/projects/details/62098505-de86-43b2-bead-ae8018854141 ESTCP project ER20-5198]<ref name="CrownoverEtAl2023">Crownover, E., Heron, G., Pennell, K., Ramsey, B., Rickabaugh, T., Stallings, P., Stauch, L., Woodcock, M., 2023. Ex Situ Thermal Treatment of PFAS-Impacted Soils, [[Media: ER20-5198 Final Report.pdf | Final Report.]] Eielson Air Force Base, Alaska. [https://serdp-estcp.mil/ Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP)], [https://serdp-estcp.mil/projects/details/62098505-de86-43b2-bead-ae8018854141 Project ER20-5198 Website]</ref>)=== |
| | + | [[File: HeronFig1.png | thumb | 400 px | Figure 1. TCH treatment of a PFAS-laden stockpile at Eielson AFB, Alaska<ref name="CrownoverEtAl2023"/>]] |
| | + | Since there has been no approved or widely accepted method for treating soils impacted by PFAS, a common practice has been to excavate PFAS-impacted soil and place it in lined stockpiles. Eielson AFB in Alaska is an example where approximately 50 stockpiles were constructed to temporarily store 150,000 cubic yards of soil. One of the stockpiles containing 134 cubic yards of PFAS-impacted soil was heated to 350-450°C over 90 days (Figure 1). Volatilized PFAS was extracted from the soil using vacuum extraction and treated via condensation and filtration by granular activated charcoal. Under field conditions, PFAS concentration reductions from 230 µg/kg to below 0.5 µg/kg were demonstrated for soils that reached 400°C or higher for 7 days. These soils achieved the Alaska soil standards of 3 µg/kg for PFOS and 1.7 µg/kg for PFOA. Cooler soils near the top of the stockpile had remaining PFOS in the range of 0.5-20 µg/kg with an overall average of 4.1 µg/kg. Sampling of all soils heated to 400°C or higher demonstrated that the soils achieved undetectable levels of targeted PFAS (typical reporting limit was 0.5 µg/kg). |
| | | | |
| − | A consequence of the helical structure is that there is limited carbon-carbon bond rotation within the perfluoroalkyl chain giving them increased rigidity compared to alkyl chains<ref>Barton, S.W., Goudot, A., Bouloussa, O., Rondelez, F., Lin, B., Novak, F., Acero, A., Rice, S., 1992. Structural transitions in a monolayer of fluorinated amphiphile molecules. The Journal of Chemical Physics, 96(2), pp. 1343-1351. [https://doi.org/10.1063/1.462170 doi: 10.1063/1.462170]</ref>. The bulkiness of the perfluoroalkyl chain confers a cylindrical shape on the fluorosurfactant amphiphile and therefore favors the formation of bilayers and vesicles the aggregation of which is further assisted by the rigidity of the molecules which allow close packing in the supramolecular structure. Fluorosurfactants therefore cannot be regarded as more hydrophobic analogues of hydrogenated surfactants. Their self-assembly behavior is characterized by a strong tendency to form vesicles and lamellar phases rather than micelles, due to the bulkiness and rigidity of the perfluoroalkyl chain that tends to decrease the curvature of the aggregates they form in solution<ref>Barton, C.A., Butler, L.E., Zarzecki, C.J., Flaherty, J., Kaiser, M., 2006. Characterizing Perfluorooctanoate in Ambient Air near the Fence Line of a Manufacturing Facility: Comparing Modeled and Monitored Values. Journal of the Air and Waste Management Association, 56, pp. 48-55. [https://doi.org/10.1080/10473289.2006.10464429 doi: 10.1080/10473289.2006.10464429] [https://www.tandfonline.com/doi/epdf/10.1080/10473289.2006.10464429?needAccess=true Open Access Article]</ref>. The larger tail cross section of fluorinated compared to hydrogenated amphiphiles tends to favor the formation of aggregates with lesser surface curvature, therefore rather than micelles they form bilayer membranes, vesicles, tubules and fibers<ref>Krafft, M.P., Guilieri, F., Riess, J.G., 1993. Can Single-Chain Perfluoroalkylated Amphiphiles Alone form Vesicles and Other Organized Supramolecular Systems? Angewandte Chemie International Edition in English, 32(5), pp. 741-743. [https://doi.org/10.1002/anie.199307411 doi: 10.1002/anie.199307411]</ref><ref>Furuya, H., Moroi, Y., Kaibara, K., 1996. Solid and Solution Properties of Alkylammonium Perfluorocarboxylates. The Journal of Physical Chemistry, 100(43), pp. 17249-17254. [https://doi.org/10.1021/jp9612801 doi: 10.1021/jp9612801]</ref><ref>Giulieri, F., Krafft, M.P., 1996. Self-organization of single-chain fluorinated amphiphiles with fluorinated alcohols. Thin Solid Films, 284-285, pp. 195-199. [https://doi.org/10.1016/S0040-6090(95)08304-9 doi: 10.1016/S0040-6090(95)08304-9]</ref><ref>Gladysz, J.A., Curran, D.P., Horvath, I.T., 2004. Handbook of Fluorous Chemistry. WILEY-VCH Verlag GmbH & Co. KGaA,, Weinheim, Germany. ISBN: 3-527-30617-X</ref>. Rojas ''et al.'' (2002) demonstrated that perfluorooctyl sulphonamide formed a contiguous bilayer at 50 mg/L with self-assembled aggregates present at concentrations as low as 10 mg/L<ref name="RojasEtAl2002">Rojas, O.J., Macakova, L., Blomberg, E., Emmer, A., and Claesson, P.M., 2002. Fluorosurfactant Self-Assembly at Solid/Liquid Interfaces. Langmuir, 18(21), pp. 8085-8095. [https://doi.org/10.1021/la025989c doi: 10.1021/la025989c]</ref>.
| + | ===''In situ'' Vadose Zone Treatment, Beale AFB, California ([https://serdp-estcp.mil/projects/details/94949542-f9f7-419d-8028-8ba318495641/er20-5250-project-overview ESTCP project ER20-5250]<ref name="Iery2024">Iery, R. 2024. In Situ Thermal Treatment of PFAS in the Vadose Zone. [https://serdp-estcp.mil/ Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP)], [https://serdp-estcp.mil/projects/details/94949542-f9f7-419d-8028-8ba318495641 Project ER20-5250 Website]. [[Media: ER20-5250 Fact Sheet.pdf | Fact Sheet.pdf]]</ref>)=== |
| | + | [[File: HeronFig2.png | thumb | 600 px | Figure 2. ''In situ'' TCH treatment of a PFAS-rich vadose zone hotspot at Beale AFB, California]] |
| | + | A former fire-training area at Beale AFB had PFAS concentrations as high as 1,970 µg/kg in shallow soils. In situ treatment of a PFAS-rich soil was demonstrated using 16 TCH borings installed in the source area to a depth of 18 ft (Figure 2). Soils which reached the target temperatures were reduced to PFAS concentrations below 1 µg/kg. Perched water which entered in one side of the area delayed heating in that area, and soils which were affected had more modest PFAS concentration reductions. As a lesson learned, future in situ TCH treatments will include provisions for minimizing water entering the treated volume<ref name="Iery2024"/>. It was demonstrated that with proper water management, even highly impacted soils can be treated to near non-detect concentrations (greater than 99% reduction). |
| | | | |
| − | ==Thermodynamics of PFAS Accumulations on Solid Surfaces== | + | ===Constructed Pile Treatment, JBER, Alaska ([https://serdp-estcp.mil/projects/details/eb7311db-6233-4c7f-b23a-e003ac1926c5/pfas-treatment-in-soil-using-thermal-conduction-heating ESTCP Project ER23-8369]<ref name="CrownoverHeron2024">Crownover, E., Heron, G., 2024. PFAS Treatment in Soil Using Thermal Conduction Heating. Defense Innovation Unit (DIU) and [https://serdp-estcp.mil/ Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP)], [https://serdp-estcp.mil/projects/details/eb7311db-6233-4c7f-b23a-e003ac1926c5/pfas-treatment-in-soil-using-thermal-conduction-heating Project ER23-8369 Website]</ref>)=== |
| − | The thermodynamics of formation of amphiphiles into supramolecular species requires consideration of both hydrophobic and hydrophilic interactions resulting from the amphoteric nature of the molecule. The hydrophilic portions of the molecule are driven to maximize their solvation interaction with as many water molecules as possible, whereas the hydrophobic portions of the molecule are driven to aggregate together thus minimizing interaction with the bulk water. Both of these processes change the [[wikipedia:Enthalpy|enthalpy]] and [[wikipedia: Entropy|entropy]] of the system.
| + | [[File: HeronFig3.png | thumb | 600 px | Figure 3. Treatment of a 2,000 cubic yard soil pile at JBER, Alaska]] |
| | + | In 2024, a stockpile of 2,000 cubic yards of PFAS-impacted soil was thermally treated at Joint Base Elmendorf-Richardson (JBER) in Anchorage, Alaska<ref name="CrownoverHeron2024"/>. This ESTCP project was implemented in partnership with DOD’s Defense Innovation Unit (DIU). Three technology demonstrations were conducted at the site where approximately 6,000 cy of PFAS-impacted soil was treated (TCH, smoldering and kiln-style thermal desorption). Figure 3 shows the fully constructed pile used for the TCH demonstration. In August 2024 the soil temperature for the TCH treatment exceeded 400°C in all monitoring locations. At an energy density of 355 kWh/cy, Alaska Department of Environmental Conservation (ADEC) standards and EPA Residential Regional Screening Levels (RSLs) for PFAS in soil were achieved. At JBER, all 30 post-treatment soil samples were near or below detection limits for all targeted PFAS compounds using EPA Method 1633. The composite of all 30 soil samples was below all detection limits for EPA Method 1633. Detection limits ranged from 0.0052 µg/kg to 0.19 µg/kg. |
| | | | |
| − | <center><big>Anion Exchange Reaction: '''PFAS<sup>-</sup></big><sub>(aq)</sub><big> + Cl<sup>-</sup></big><sub>(resin bound)</sub><big> ⇒ PFAS<sup>-</sup></big><sub>(resin bound)</sub><big> + Cl<sup>-</sup></big><sub>(aq)</sub>'''</center>
| + | ==Advantages and Disadvantages== |
| | + | Thermal treatment of PFAS in soils is energy intensive, and the cost of that energy may be prohibitive for some clients. Also, while it often is the least costly option for complete PFAS removal when compared to excavation followed by offsite disposal or destruction, heating soil to treatment temperatures on site or ''in situ'' typically takes longer than excavation. Major advantages include: |
| | + | *On site or ''in situ'' treatment eliminates the need to transport and dispose of the contaminated soil |
| | + | *Site liabilities are removed once and for all |
| | + | *Treatment costs are competitive with excavation, transportation and off-site treatment or disposal. |
| | | | |
| − | {| class="wikitable mw-collapsible" style="float:left; margin-right:20px; text-align:center;"
| + | ==Recommendations== |
| − | |+Table 1. Percent decreases from initial PFAS concentrations during benchtop testing of PRD treatment in different water matrices
| + | Recent research suggests: |
| − | |-
| + | *Successful thermal treatment of PFAS may require a higher target temperature than for other organics with similar boiling points |
| − | ! Analytes
| + | *Prevention of influx of water into treatment zone may be necessary. |
| − | !
| + | Future studies should examine the potential for enhanced degradation during the thermal process by using soil amendments and/or manipulation of the local geochemistry to reduce the required treatment temperatures and therefore also reduce energy demand. |
| − | ! GW
| |
| − | ! FF
| |
| − | ! AFFF<br>Rinsate
| |
| − | ! AFF<br>(diluted 10X)
| |
| − | ! IDW NF
| |
| − | |-
| |
| − | | Σ Total PFAS<small><sup>a</sup></small> (ND=0)
| |
| − | | rowspan="9" style="background-color:white;" | <p style="writing-mode: vertical-rl">% Decrease<br>(Initial Concentration, μg/L)</p>
| |
| − | | 93%<br>(370) || 96%<br>(32,000) || 89%<br>(57,000) || 86 %<br>(770,000) || 84%<br>(82)
| |
| − | |-
| |
| − | | Σ Total PFAS (ND=MDL) || 93%<br>(400) || 86%<br>(32,000) || 90%<br>(59,000) || 71%<br>(770,000) || 88%<br>(110)
| |
| − | |-
| |
| − | | Σ Total PFAS (ND=RL) || 94%<br>(460) || 96%<br>(32,000) || 91%<br>(66,000) || 34%<br>(770,000) || 92%<br>(170)
| |
| − | |-
| |
| − | | Σ Highly Regulated PFAS<small><sup>b</sup></small> (ND=0) || >99%<br>(180) || >99%<br>(20,000) || 95%<br>(20,000) || 92%<br>(390,000) || 95%<br>(50)
| |
| − | |-
| |
| − | | Σ Highly Regulated PFAS (ND=MDL) || >99%<br>(180) || 98%<br>(20,000) || 95%<br>(20,000) || 88%<br>(390,000) || 95%<br> (52)
| |
| − | |-
| |
| − | | Σ Highly Regulated PFAS (ND=RL) || >99%<br>(190) || 93%<br>(20,000) || 95%<br>(20,000) || 79%<br>(390,000) || 95%<br>(55)
| |
| − | |-
| |
| − | | Σ Priority PFAS<small><sup>c</sup></small> (ND=0) || 91%<br>(180) || 98%<br>(20,000) || 85%<br>(20,000) || 82%<br>(400,000) || 94%<br>(53)
| |
| − | |-
| |
| − | | Σ Priority PFAS (ND=MDL) || 91%<br>(190) || 94%<br>(20,000) || 85%<br>(20,000) || 79%<br>(400,000) || 86%<br>(58)
| |
| − | |-
| |
| − | | Σ Priority PFAS (ND=RL) || 92%<br>(200) || 87%<br>(20,000) || 86%<br>(21,000) || 70%<br>(400,000) || 87%<br>(65)
| |
| − | |-
| |
| − | | Fluorine mass balance<small><sup>d</sup></small> || ||106% || 109% || 110% || 65% || 98%
| |
| − | |-
| |
| − | | Sorbed organic fluorine<small><sup>e</sup></small> || || 4% || 4% || 33% || N/A || 31%
| |
| − | |-
| |
| − | | colspan="7" style="background-color:white; text-align:left" | <small>Notes:<br>GW = groundwater<br>GW FF = groundwater foam fractionate<br>AFFF rinsate = rinsate collected from fire system decontamination<br>AFFF (diluted 10x) = 3M Lightwater AFFF diluted 10x<br>IDW NF = investigation derived waste nanofiltrate<br>ND = non-detect<br>MDL = Method Detection Limit<br>RL = Reporting Limit<br><small><sup>a</sup></small>Total PFAS = 40 analytes + unidentified PFCA precursors<br><small><sup>b</sup></small>Highly regulated PFAS = PFNA, PFOA, PFOS, PFHxS, PFBS, HFPO-DA<br><small><sup>c</sup></small>High priority PFAS = PFNA, PFOA, PFHxA, PFBA, PFOS, PFHxS, PFBS, HFPO-DA<br><small><sup>d</sup></small>Ratio of the final to the initial organic fluorine plus inorganic fluoride concentrations<br><small><sup>e</sup></small>Percent of organic fluorine that sorbed to the reactor walls during treatment<br></small>
| |
| − | |}
| |
| − | | |
| − | | |
| − | In aqueous solution, the hydrophilic portions of an amphiphile form hydrogen bonds (4 - 120 kJ/mol) and van der Waals interactions (<5 kJ/mol) with water molecules and surfaces, and electrostatic interactions (5 – 300 kJ/mol) can also occur where the amphiphile is ionic<ref name="LombardoEtAl2015">Lombardo, D., Kiselev, M.A., Magazù, S., Calandra, P., 2015. Amphiphiles Self-Assembly: Basic Concepts and Future Perspectives of Supramolecular Approaches. Advances in Condensed Matter Physics, vol. 2015, article ID 151683, 22 pages. [https://doi.org/10.1155/2015/151683 doi: 10.1155/2015/151683] [[Media: LombardoEtAl2015.pdf | Open Access Article]]</ref>. These interactions, although weak compared to intramolecular covalent bonds within a molecule are energetically favorable and increase the enthalpy of the combined solute-solvent system. Thus, the hydrophilic portion of an amphiphile will look to maximize enthalpic gain through hydrogen bond interactions with the bulk water.
| |
| − | | |
| − | The hydrophobic portion of an amphiphile cannot form hydrogen bonds with the bulk solution, and its presence disrupts the hydrogen bond interactions between individual water molecules within the bulk water matrix. This disruption lowers the entropy of the system by reducing the degrees of translational rotational freedom available to the bulk water. The [[wikipedia:Second law of thermodynamics|second law of thermodynamics]] dictates that a system will arrange itself to maximize its entropy. With hydrophobic species this can be achieved by their spontaneous aggregation, as the reduction in solution entropy of the aggregated system is less than that which would occur if the component parts were solvated individually. These hydrophobic and hydrophilic interactions are weak, and the individual entropy gain per amphiphile upon aggregation is very small. However, taken together the overall effect on the entropy of the aggregate is sufficient to maintain it in solution, and moreover these interactions make the aggregates resistant to minor perturbations while retaining the reversibility of the self-assembled structure<ref name="LombardoEtAl2015"/>.
| |
| − | | |
| − | ==Regulatory Drivers for Transition to PFAS-Free Firefighting Formulations==
| |
| − | Regulations restricting the use and release of PFAS are being proposed and promulgated worldwide, with several enacted regulations addressing the use of aqueous film forming foams (AFFF) containing PFAS<ref name="Queensland2016">Queensland (Australia) Department of Environment and Heritage Protection, 2016. Operational Policy - Environmental Management of Firefighting Foam. 16 pages. [https://environment.des.qld.gov.au/assets/documents/regulation/firefighting-foam-policy.pdf Free Download]</ref><ref>U.S. Congress, 2019. S.1790 - National Defense Authorization Act for Fiscal Year 2020. United States Library of Congress. [https://www.congress.gov/bill/116th-congress/senate-bill/1790 Text and History of Law].</ref><ref>Arizona State Legislature, 2019. Title 36, Section 1696. Firefighting foam; prohibited uses; exception; definitions. [https://www.azleg.gov/viewdocument/?docName=https://www.azleg.gov/ars/36/01696.htm Text of Law]</ref><ref>California Legislature, 2020. Senate Bill No. 1044, Chapter 308, Firefighting equipment and foam: PFAS chemicals. [https://leginfo.legislature.ca.gov/faces/billTextClient.xhtml?bill_id=201920200SB1044 Text and History of Law]</ref><ref>Arkansas General Assembly, 2021. An Act Concerning the Use of Certain Chemicals in Firefighting Foam; and for Other Purposes. Act 315, State of Arkansas. [https://trackbill.com/bill/arkansas-house-bill-1351-concerning-the-use-of-certain-chemicals-in-firefighting-foam/2008913/ Text and History of Law].</ref><ref>Espinosa, Summers, Kelly, J., Statler, Hansen, Young, 2021. Amendment to Fire Prevention and Control Act. House Bill 2722. West Virginia Legislature. [https://trackbill.com/bill/west-virginia-house-bill-2722-prohibiting-the-use-of-class-b-fire-fighting-foam-for-testing-purposes-if-the-foam-contains-a-certain-class-of-fluorinated-organic-chemicals/2047674/ Text and History of Law]</ref><ref>Louisiana Legislature, 2021. Act No. 232. [https://trackbill.com/bill/louisiana-house-bill-389-fire-protect-fire-marshal-provides-relative-to-the-discharge-or-use-of-class-b-fire-fighting-foam-containing-fluorinated-organic-chemicals/2092535/ Text and History of Law]</ref><ref>Vermont Legislature, 2021b. Act No. 36, PFAS in Class B Firefighting Foam. [https://trackbill.com/bill/vermont-senate-bill-20-an-act-relating-to-restrictions-on-perfluoroalkyl-and-polyfluoroalkyl-substances-and-other-chemicals-of-concern-in-consumer-products/1978963/ History and Text of Law]</ref>. In addition to regulated usage, firefighting formulation users are transitioning to PFAS-free firefighting formulations to reduce environmental liability in the event of a release, to reduce the cost of expensive containment systems and management of generated waste streams, and to avoid reputational damage. In 2016, Queensland, Australia was one of the first governments to ban PFAS use in firefighting foam<ref name="Queensland2016"/>. The US 2020 National Defense Authorization Act specified immediate prohibition of controlled releases of AFFF containing PFAS and required the Secretary of the Navy to publish a specification for PFAS-free firefighting formulation use and ensure it is available for use by the Department of Defense (DoD) by October 1, 2023<ref>U.S. Congress, 2021. S.2792 - National Defense Authorization Act for Fiscal Year 2021. United States Library of Congress. [https://www.congress.gov/bill/117th-congress/senate-bill/2792/ Text and History of Law].</ref>. The National Fire Protection Association (NFPA) recently removed the requirement for AFFF containing PFAS from their Standard on Aircraft Hangars and added two new chapters to allow users to determine if AFFF containing PFAS is needed at their facility<ref name="NFPA2022">National Fire Protection Association (NFPA), 2022. Codes and Standards, 409: Standard on Aircraft Hangars. [https://www.nfpa.org/codes-and-standards/4/0/9/409?l=42 NFPA Website]</ref>.
| |
| − | | |
| − | ==Selection of Replacement PFAS-Free Firefighting Formulations==
| |
| − | Since they first entered the market in the 2000s, the operational capabilities of PFAS-free firefighting formulations have grown<ref>Allcorn, M., Bluteau, T., Corfield, J., Day, G., Cornelsen, M., Holmes, N.J.C., Klein, R.A., McDowall, J.G., Olsen, K.T., Ramsden, N., Ross, I., Schaefer, T.H., Weber, R., Whitehead, K., 2018. Fluorine-Free Firefighting Foams (3F) – Viable Alternatives to Fluorinated Aqueous Film-Forming Foams (AFFF). White Paper prepared for the IPEN by members of the IPEN F3 Panel and associates, POPRC-14, Rome. [https://ipen.org/sites/default/files/documents/IPEN_F3_Position_Paper_POPRC-14_12September2018d.pdf Free Download].</ref> and numerous companies are now manufacturing and delivering PFAS-free firefighting formulations for fixed systems and AFFF vehicles<ref>Ansul (Company), Ansul NFF-331 3%x3% Non-Fluorinated Foam Concentrate (Commercial Product). [https://docs.johnsoncontrols.com/specialhazards/api/khub/documents/1nbeVfynU1IW~eJcCOA0Bg/content Product Data Sheet].</ref><ref>BioEx (Company), Ecopol A+ (Commercial Product). [https://www.bio-ex.com/en/our-products/product/ecopol-aplus/ Website]</ref><ref>National Foam (Company), 2020. Avio F3 Green KHC 3%, Fluorine Free Foam Concentrate (Commercial Product). [https://nationalfoam.com/wp-content/uploads/sites/4/NMS515-Avio-Green-KHC-3-FF.pdf Safety Data Sheet]</ref>. Key factors in the selection of a PFAS-free firefighting formulation product are compatibility of the new formulation with the existing system (as confirmed by a fire protection engineer) and environmental certifications (i.e., verifying the absence of organic fluorine or PFAS or the absence of other non-fluorine environmental contaminants).
| |
| − | | |
| − | In January 2023, the US Department of Defense (DoD) published the [https://media.defense.gov/2023/Jan/12/2003144157/-1/-1/1/MILITARY-SPECIFICATION-FOR-FIRE-EXTINGUISHING-AGENT-FLUORINE-FREE-FOAM-F3-LIQUID-CONCENTRATE-FOR-LAND-BASED-FRESH-WATER-APPLICATIONS.PDF Performance Specification for Fire Extinguishing Agent, Fluorine-Free Foam (F3) Liquid Concentrate for Land-Based, Fresh Water Applications]<ref name="DoD2023"/>. This Military Performance Specification (Mil-Spec) allows PFAS-free firefighting formulations to be certified as meeting certain standardized operational goals for use in military settings. In addition to Mil-Spec requirements, PFAS-free firefighting formulations can also be certified through Underwriters Laboratories Standard for Safety, Foam Equipment and Liquid Concentrates, UL 162, which requires the new firefighting formulations be investigated for suitability and compatibility with the specific equipment with which they are intended to be used<ref>Underwriters Laboratories Inc., 2018. UL162, UL Standard for Safety, Foam Equipment and Liquid Concentrates, 8th Edition, Revised 2022. 40 pages. [https://global.ihs.com/doc_detail.cfm?document_name=UL%20162&item_s_key=00096960 Website]</ref>. Several PFAS-free foams have been certified under various parts of EN1568, the European Standard which specifies the necessary foam properties and performance requirements<ref>European Standards, 2018. CSN EN 1568-1 ed. 2: Fire extinguishing media - Foam concentrates - Part 1: Specification for medium expansion foam concentrates for surface application to water-immiscible liquids. 48 pages. [https://www.en-standard.eu/csn-en-1568-1-ed-2-fire-extinguishing-media-foam-concentrates-part-1-specification-for-medium-expansion-foam-concentrates-for-surface-application-to-water-immiscible-liquids/ European Standards Website.]</ref>. Both [https://serdp-estcp.mil/ ESTCP and SERDP] have supported (and continue to support) the development and field validation of PFAS-free firefighting formulations (e.g. [https://serdp-estcp.mil/projects/details/baa72637-e3c8-40ee-a007-f295311c72ad WP22-7456], [https://serdp-estcp.mil/projects/details/1bed98f7-dbe6-4bdd-98d2-1f9cfeb5f3d9/wp21-3465-project-overview WP21-3465], [https://serdp-estcp.mil/projects/details/bc932800-cfc8-4e86-a212-5f8c9d27f17c WP20-1535]). Both the US Federal Aviation Administration (FAA) and National Fire Protection Association (NFPA) have performed a variety of foam certification tests on numerous PFAS-free firefighting formulations<ref>Back, G.G., Farley, J.P., 2020. Evaluation of the Fire Protection Effectiveness of Fluorine Free Firefighting Foams. National Fire Protection Association, Fire Protection Research Foundation. [https://www.iafc.org/docs/default-source/1safehealthshs/effectivenessofflourinefreefoam.pdf Free Download].</ref><ref>Casey, J., Trazzi, D., 2022. Fluorine-Free Foam Testing. Federal Aviation Administration (FAA) Final Report. [https://www.airporttech.tc.faa.gov/DesktopModules/EasyDNNNews/DocumentDownload.ashx?portalid=0&moduleid=3682&articleid=2882&documentid=3054 Open Access Article]</ref>.
| |
| − | | |
| − | ==Selection of Flushing Agent==
| |
| − | General industry guidance has typically recommended several rinses with water to remove PFAS from impacted equipment. Owing to the unique physical and chemical properties of PFAS, the use of room temperature water to remove PFAS from impacted equipment has not been very effective. To address these recalcitrant accumulations, companies are developing new methods to remove self-assembled PFAS bilayers from existing fire-fighting infrastructure so that it can be successfully transitioned to PFAS-free formulations. Arcadis developed a non-toxic cleaning agent, Fluoro Fighter<sup>TM</sup>, which has been demonstrated to be effective for removal of PFAS from equipment by disrupting the accumulated layers of PFAS coating the AFFF-wetted surfaces.
| |
| − | | |
| − | Laboratory studies have supported the optimization of this PFAS removal method in fire suppression system piping obtained from a commercial airport hangar in Sydney, Australia<ref name="LangEtAl2022"/>. Prior to removal from the hangar, the stainless-steel pipe held PFAS-containing AFFF for more than three decades. Results indicated that Fluoro Fighter<sup>TM</sup>, as well as flushing at elevated temperatures, removed more surface associated PFAS in comparison to equivalent extractions using methanol or water at room temperature. ESTCP has supported (and continues to support) the development and field validation of best practices for methodologies to clean foam delivery systems (e.g. [https://serdp-estcp.mil/projects/details/1521652f-a8b2-4c52-9232-c1018989a6b1 ER20-5364], [https://serdp-estcp.mil/projects/details/6d0750be-f20b-4765-bdfa-872adccaf37a ER20-5361], [https://serdp-estcp.mil/projects/details/0aa2fb20-b851-4b5b-ac64-e72795986b8a ER20-5369], [https://serdp-estcp.mil/projects/details/4fd2e4ab-ddb7-40f8-835e-e1d637c0d650 ER21-7229]).
| |
| − | | |
| − | ==PFAS Verification Testing==
| |
| − | In general, PFAS sampling techniques used to support firefighting formulation transition activities are consistent with conventional sampling techniques used in the environmental industry, but special consideration is made regarding high concentration PFAS materials, elevated detection levels, cross-contamination potential, precursor content, and matrix interferences. The analytical method selected should be appropriate for the regulatory requirements in the site area.
| |
| − | | |
| − | ==Rinsate Treatment==
| |
| − | Numerous technologies for treatment of PFAS-impacted water sources, including rinsates, have been and are currently being developed. These include separation technologies such as [[PFAS Ex Situ Water Treatment|foam fractionation, nanofiltration, sorbents/flocculants, ion exchange resins, reverse osmosis, and destructive technologies such as sonolysis, electrochemical oxidation, hydrothermal alkaline treatment]], [[PFAS Treatment by Electrical Discharge Plasma |enhanced contact plasma]], and [[Supercritical Water Oxidation (SCWO) |supercritical water oxidation (SCWO)]]. Many of these technologies have rapidly developed from bench-scale (e.g., microcosms, columns, single reactors) to commercially available field-scale units capable of managing PFAS-impacted waters of varying waste volumes and PFAS compositions and concentrations. Ongoing field research continues to improve the treatment efficiency, reliability, and versatility of these technologies, both individually and as coupled treatment solutions (e.g., treatment train). ESTCP has supported (and continues to support) the development and field validation of separation and destructive technologies for treatment of PFAS-impacted water sources, including rinsates (e.g. [https://serdp-estcp.mil/projects/details/0c7af048-3a00-471f-9480-292aa78ecd4f ER20-5370], [https://serdp-estcp.mil/projects/details/0aa2fb20-b851-4b5b-ac64-e72795986b8a ER20-5369], [https://serdp-estcp.mil/projects/details/0d7c91a8-d755-4876-a8bb-c3e896feee0d ER20-5350], [https://serdp-estcp.mil/projects/details/790e2dda-1f7b-4ff5-b77e-08ed10a456b1 ER20-5355]).
| |
| − | | |
| − | Remedy selection for treatment of rinsates involves several key factors. It is critical that environmental practitioners have up-to-date technical and practical knowledge on the suitability of these remedial options for different site conditions, treatment volumes, PFAS composition (e.g., presence of precursors, co-contaminants), PFAS concentrations, safety considerations, potential for undesired byproducts (e.g., perchlorate, disinfection byproducts), and treatment costs (e.g., energy demand, capital costs, operational labor).
| |
| | | | |
| | ==References== | | ==References== |
| Line 158: |
Line 62: |
| | | | |
| | ==See Also== | | ==See Also== |
| − | [https://portal.ct.gov/-/media/CFPC/KO/2022/Latest-News/DESPP-DEEP-AFFF-MuniFDupdate-2022-05-26.pdf Connecticut Take-Back Program for municipal fire departments using AFFF containing PFAS]
| |
| − |
| |
| − | [https://www.arcadis.com/en-us/knowledge-hub/blog/united-states/johnsie-lang/2021/transitioning-to-pfas-free-firefighting Arcadis blog on Fluoro Fighter<sup>TM</sup>]
| |
| − |
| |
| − | [https://serdp-estcp.mil/projects/details/1521652f-a8b2-4c52-9232-c1018989a6b1 Project Summary ESTCP ER20-5634: Demonstration and Validation of Environmentally Sustainable Methods to Effectively Remove PFAS from Fire Suppression Systems]
| |
| − |
| |
| − | [https://serdp-estcp.org/projects/details/0d7c91a8-d755-4876-a8bb-c3e896feee0d Project Summary ESTCP ER20-5350: Supercritical Water Oxidation (SCWO) for Complete PFAS Destruction]
| |
Thermal Conduction Heating for Treatment of PFAS-Impacted Soil
Removal of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) compounds from impacted soils is challenging due to the modest volatility and varying properties of most PFAS compounds. Thermal treatment technologies have been developed for treatment of semi-volatile compounds in soils such as dioxins, furans, poly-aromatic hydrocarbons and poly-chlorinated biphenyls at temperatures near 325°C. In controlled bench-scale testing, complete removal of targeted PFAS compounds to concentrations below reporting limits of 0.5 µg/kg was demonstrated at temperatures of 400°C[1]. Three field-scale thermal PFAS treatment projects that have been completed in the US include an in-pile treatment demonstration, an in situ vadose zone treatment demonstration and a larger scale treatment demonstration with excavated PFAS-impacted soil in a constructed pile. Based on the results, thermal treatment temperatures of at least 400°C and a holding time of 7-10 days are recommended for reaching local and federal PFAS soil standards. The energy requirement to treat typical wet soil ranges from 300 to 400 kWh per cubic yard, exclusive of heat losses which are scale dependent. Extracted vapors have been treated using condensation and granular activated charcoal filtration, with thermal and catalytic oxidation as another option which is currently being evaluated for field scale applications. Compared to other options such as soil washing, the ability to treat on site and to treat all soil fractions is an advantage.
Related Article(s):
Contributors: Gorm Heron, Emily Crownover, Patrick Joyce, Ramona Iery
Key Resource:
- Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation[1]
Introduction
Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) have become prominent emerging contaminants in soil and groundwater. Soil source zones have been identified at locations where the chemicals were produced, handled or used. Few effective options exist for treatments that can meet local and federal soil standards. Over the past 30 plus years, thermal remediation technologies have grown from experimental and innovative prospects to mature and accepted solutions deployed effectively at many sites. More than 600 thermal case studies have been summarized by Horst and colleagues[2]. Thermal Conduction Heating (TCH) has been used for higher temperature applications such as removal of 1,4-Dioxane. This article reports recent experience with TCH treatment of PFAS-impacted soil.
Target Temperature and Duration
PFAS behave differently from most other organics subjected to TCH treatment. While the boiling points of individual PFAS fall in the range of 150-400°C, their chemical and physical behavior creates additional challenges. Some PFAS form ionic species in certain pH ranges and salts under other chemical conditions. This intricate behavior and our limited understanding of what this means for our ability to remove the PFAS from soils means that direct testing of thermal treatment options is warranted. Crownover and colleagues[1] subjected PFAS-laden soil to bench-scale heating to temperatures between 200 and 400°C which showed strong reductions of PFAS concentrations at 350°C and complete removal of many PFAS compounds at 400°C. The soil concentrations of targeted PFAS were reduced to nearly undetectable levels in this study.
Heating Method
For semi-volatile compounds such as dioxins, furans, poly-chlorinated biphenyls (PCBs) and Poly-Aromatic Hydrocarbons (PAH), thermal conduction heating has evolved as the dominant thermal technology because it is capable of achieving soil temperatures higher than the boiling point of water, which are necessary for complete removal of these organic compounds. Temperatures between 200 and 500°C have been required to achieve the desired reduction in contaminant concentrations[3]. TCH has become a popular technology for PFAS treatment because temperatures in the 400°C range are needed.
The energy source for TCH can be electricity (most commonly used), or fossil fuels (typically gas, diesel or fuel oil). Electrically powered TCH offers the largest flexibility for power input which also can be supplied by renewable and sustainable energy sources.
Energy Usage
Treating PFAS-impacted soil with heat requires energy to first bring the soil and porewater to the boiling point of water, then to evaporate the porewater until the soil is dry, and finally to heat the dry soil up to the target treatment temperature. The energy demand for wet soils falls in the 300-400 kWh/cy range, dependent on porosity and water saturation. Additional energy is consumed as heat is lost to the surroundings and by vapor treatment equipment, yielding a typical usage of 400-600 kWh/cy total for larger soil treatment volumes. Wetter soils and small treatment volumes drive the energy usage towards the higher number, whereas larger soil volumes and dry soil can be treated with less energy.
Vapor Treatment
During the TCH process a significant fraction of the PFAS compounds are volatilized by the heat and then removed from the soil by vacuum extraction. The vapors must be treated and eventually discharged while meeting local and/or federal standards. Two types of vapor treatment have been used in past TCH applications for organics: (1) thermal and catalytic oxidation and (2) condensation followed by granular activated charcoal (GAC) filtration. Due to uncertainties related to thermal destruction of fluorinated compounds and future requirements for treatment temperature and residence time, condensation and GAC filtration have been used in the first three PFAS treatment field demonstrations. It should be noted that PFAS compounds will stick to surfaces and that decontamination of the equipment is important. This could generate additional waste as GAC vessels, pipes and other wetted equipment need careful cleaning with solvents or rinsing agents such as PerfluorAdTM.
PFAS Reactivity and Fate
While evaluating initial soil treatment results, Crownover et al[1] noted the lack of complete data sets when the soils were analyzed for non-targeted compounds or extractable precursors. Attempts to establish the fluorine balance suggest that the final fate of the fluorine in the PFAS is not yet fully understood. Transformations are likely occurring in the heated soil as demonstrated in laboratory experiments with and without calcium hydroxide (Ca(OH)2) amendment[4]. Amendments such as Ca(OH)2 may be useful in reducing the required treatment temperature by catalyzing PFAS degradation. With thousands of PFAS potentially present, the interactions are complex and may never be fully understood. Therefore, successful thermal treatment may require a higher target temperature than for other organics with similar boiling points – simply to provide a buffer against the uncertainty.
Case Studies
Figure 1. TCH treatment of a PFAS-laden stockpile at Eielson AFB, Alaska
[5]Since there has been no approved or widely accepted method for treating soils impacted by PFAS, a common practice has been to excavate PFAS-impacted soil and place it in lined stockpiles. Eielson AFB in Alaska is an example where approximately 50 stockpiles were constructed to temporarily store 150,000 cubic yards of soil. One of the stockpiles containing 134 cubic yards of PFAS-impacted soil was heated to 350-450°C over 90 days (Figure 1). Volatilized PFAS was extracted from the soil using vacuum extraction and treated via condensation and filtration by granular activated charcoal. Under field conditions, PFAS concentration reductions from 230 µg/kg to below 0.5 µg/kg were demonstrated for soils that reached 400°C or higher for 7 days. These soils achieved the Alaska soil standards of 3 µg/kg for PFOS and 1.7 µg/kg for PFOA. Cooler soils near the top of the stockpile had remaining PFOS in the range of 0.5-20 µg/kg with an overall average of 4.1 µg/kg. Sampling of all soils heated to 400°C or higher demonstrated that the soils achieved undetectable levels of targeted PFAS (typical reporting limit was 0.5 µg/kg).
In situ Vadose Zone Treatment, Beale AFB, California (ESTCP project ER20-5250[6])
Figure 2.
In situ TCH treatment of a PFAS-rich vadose zone hotspot at Beale AFB, California
A former fire-training area at Beale AFB had PFAS concentrations as high as 1,970 µg/kg in shallow soils. In situ treatment of a PFAS-rich soil was demonstrated using 16 TCH borings installed in the source area to a depth of 18 ft (Figure 2). Soils which reached the target temperatures were reduced to PFAS concentrations below 1 µg/kg. Perched water which entered in one side of the area delayed heating in that area, and soils which were affected had more modest PFAS concentration reductions. As a lesson learned, future in situ TCH treatments will include provisions for minimizing water entering the treated volume[6]. It was demonstrated that with proper water management, even highly impacted soils can be treated to near non-detect concentrations (greater than 99% reduction).
Figure 3. Treatment of a 2,000 cubic yard soil pile at JBER, Alaska
In 2024, a stockpile of 2,000 cubic yards of PFAS-impacted soil was thermally treated at Joint Base Elmendorf-Richardson (JBER) in Anchorage, Alaska[7]. This ESTCP project was implemented in partnership with DOD’s Defense Innovation Unit (DIU). Three technology demonstrations were conducted at the site where approximately 6,000 cy of PFAS-impacted soil was treated (TCH, smoldering and kiln-style thermal desorption). Figure 3 shows the fully constructed pile used for the TCH demonstration. In August 2024 the soil temperature for the TCH treatment exceeded 400°C in all monitoring locations. At an energy density of 355 kWh/cy, Alaska Department of Environmental Conservation (ADEC) standards and EPA Residential Regional Screening Levels (RSLs) for PFAS in soil were achieved. At JBER, all 30 post-treatment soil samples were near or below detection limits for all targeted PFAS compounds using EPA Method 1633. The composite of all 30 soil samples was below all detection limits for EPA Method 1633. Detection limits ranged from 0.0052 µg/kg to 0.19 µg/kg.
Advantages and Disadvantages
Thermal treatment of PFAS in soils is energy intensive, and the cost of that energy may be prohibitive for some clients. Also, while it often is the least costly option for complete PFAS removal when compared to excavation followed by offsite disposal or destruction, heating soil to treatment temperatures on site or in situ typically takes longer than excavation. Major advantages include:
- On site or in situ treatment eliminates the need to transport and dispose of the contaminated soil
- Site liabilities are removed once and for all
- Treatment costs are competitive with excavation, transportation and off-site treatment or disposal.
Recommendations
Recent research suggests:
- Successful thermal treatment of PFAS may require a higher target temperature than for other organics with similar boiling points
- Prevention of influx of water into treatment zone may be necessary.
Future studies should examine the potential for enhanced degradation during the thermal process by using soil amendments and/or manipulation of the local geochemistry to reduce the required treatment temperatures and therefore also reduce energy demand.
References
- ^ 1.0 1.1 1.2 1.3 Crownover, E., Oberle, D., Heron, G., Kluger, M., 2019. Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation. Remediation Journal, 29(4), pp. 77-81. doi: 10.1002/rem.21623
- ^ Horst, J., Munholland, J., Hegele, P., Klemmer, M., Gattenby, J., 2021. In Situ Thermal Remediation for Source Areas: Technology Advances and a Review of the Market From 1988–2020. Groundwater Monitoring & Remediation, 41(1), p. 17. doi: 10.1111/gwmr.12424 Open Access Manuscript
- ^ Stegemeier, G.L., Vinegar, H.J., 2001. Thermal Conduction Heating for In-Situ Thermal Desorption of Soils. Ch. 4.6, pp. 1-37. In: Chang H. Oh (ed.), Hazardous and Radioactive Waste Treatment Technologies Handbook, CRC Press, Boca Raton, FL. ISBN 9780849395864 Open Access Article
- ^ Koster van Groos, P.G., 2021. Small-Scale Thermal Treatment of Investigation-Derived Wastes Containing PFAS. Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP), Project ER18-1556 Website, Final Report.pdf
- ^ 5.0 5.1 Crownover, E., Heron, G., Pennell, K., Ramsey, B., Rickabaugh, T., Stallings, P., Stauch, L., Woodcock, M., 2023. Ex Situ Thermal Treatment of PFAS-Impacted Soils, Final Report. Eielson Air Force Base, Alaska. Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP), Project ER20-5198 Website
- ^ 6.0 6.1 Iery, R. 2024. In Situ Thermal Treatment of PFAS in the Vadose Zone. Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP), Project ER20-5250 Website. Fact Sheet.pdf
- ^ 7.0 7.1 Crownover, E., Heron, G., 2024. PFAS Treatment in Soil Using Thermal Conduction Heating. Defense Innovation Unit (DIU) and Strategic Environmental Research and Development Program (SERDP) - Environmental Security Technology Certification Program (ESTCP), Project ER23-8369 Website
See Also
