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==Supercritical Water Oxidation (SCWO)==
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==Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes==  
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Supercritical water oxidation (SCWO) is a single step [[Wikipedia: Wet oxidation | wet oxidation]] process that transforms organic matter into water, carbon dioxide and, depending on the waste undergoing treatment, an inert mineral solid residue. The process is highly effective and can treat a variety of wet wastes without dewatering. The SCWO technology allows for the complete destruction of persistent and toxic organic contaminants such as [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | perfluoroalkyl and polyfluoroalkyl substances (PFAS)]], [[1,4-Dioxane | 1,4-dioxane]], and many more.  
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Thermal In Situ Sustainable Remediation (TISR<sup>®</sup>; US Pat. Nos. 10,384,246 and 10,688,545) is a cost-effective and adaptable low temperature thermal remediation technology that accelerates contaminant treatment. It achieves this by enhancing biotic and abiotic contaminant degradation rates through a modest increase in subsurface temperature. TISR<sup>®</sup> is suitable for a wide range of hydrogeologic settings. It also offers reduced operational costs, a lower carbon footprint, and possibly shorter remedial timeframes than more conventional methods.
 
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'''Related Article(s):'''
 
'''Related Article(s):'''
  
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* [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
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*[[Thermal Remediation]]
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* [[PFAS Transport and Fate]]
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*[[Thermal Remediation - Electrical Resistance Heating | Electrical Resistance Heating]]
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* [[Chlorinated Solvents]]
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*[[Thermal Conduction Heating (TCH)]]
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*[[Thermal Remediation - Combined Remedies | Combined Remedies]]
  
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'''Contributor(s):''' [[Kobe Nagar]] and [[Dr. Marc Deshusses]]
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'''Contributors:''' Jonah Munholland, Julia Vidonish, and Craig Divine
  
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'''Key Resource(s):'''
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'''Key Resources:'''
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*Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes, Final Report. ESTCP Project ER20-5028<ref>Divine, C., Munholland, J., Zardouzian, E., Justicia-Leon, S., Aspinall, J.V., Randhawa, D., Falta, R., Freedman, D., Becker, M., 2025. Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes, Final Report. Environmental Security Technology Certification Program (ESTCP), Project ER20-5028. [https://serdp-estcp.mil/projects/details/bab4bc87-b4bc-42df-ad0e-11ea0adf27dc/er20-5028-project-overview Project Website]&nbsp; [[Media: ER20-5028 FR DevineEtAl2025.pdf | Final Report.pdf]]</ref>.
  
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*Treatment of municipal sewage sludge in supercritical water: A review<ref name="Qian2016">Qian, L., Wang, S., Xu, D., Guo, Y., Tang, X., and Wang, L., 2016. Treatment of municipal sewage sludge in supercritical water: A review. Water Research, 89, pp. 118-131. [https://doi.org/10.1016/j.watres.2015.11.047 DOI: 10.1016/j.watres.2015.11.047]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Shuzhong-Wang/publication/284563832_Treatment_of_Municipal_Sewage_Sludge_in_Supercritical_Water_a_Review/links/5d9b63b6299bf1c363fef63e/Treatment-of-Municipal-Sewage-Sludge-in-Supercritical-Water-a-Review.pdf ResearchGate]</ref>.  
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*Advances in Low-Temperature Thermal Remediation. Munholland ''et al.'', 2024<ref name="MunhollandEtAl2024">Munholland, J, Rosso, D., Randhawa, D., Devine, C., Pennington, A., 2024. Advances in Low-Temperature Thermal Remediation. In: García-Rincón, J., Gatsios, E., Lenhard, R.J., Atekwana, E.A., Naidu, R. (eds), Advances in the Characterisation and Remediation of Sites Contaminated with Petroleum Hydrocarbons, Chapter 18 pp. 623-653. Environmental Contamination Remediation and Management series, Springer Nature. [https://doi.org/10.1007/978-3-031-34447-3_18 doi: 10.1007/978-3-031-34447-3_18]&nbsp; [[Media: MunhollandEtAl2024.pdf | Open Access Chapter]]</ref>.  
  
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*Supercritical Water Oxidation – Current Status of Full-scale Commercial Activity for Waste Destruction<ref name="Marrone2013">Marrone, P.A., 2013. Supercritical Water Oxidation – Current Status of Full-scale Commercial Activity for Waste Destruction. Journal of Supercritical Fluids, 79, pp. 283-288. [https://doi.org/10.1016/j.supflu.2012.12.020 DOI: 10.1016/j.supflu.2012.12.020]&nbsp;&nbsp; Author’s manuscript available from: [https://semspub.epa.gov/work/06/9545963.pdf US EPA]</ref>.
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*A Design Tool for Solar Thermal Remediation Using Borehole Heat Exchangers. Ornelles, Falta, and Divine, 2023<ref name="Ornelles">Ornelles, A.D., Falta, R.W., Divine, C.E., 2023. A Design Tool for Solar Thermal Remediation Using Borehole Heat Exchangers. Ground Water, 61(2), pp. 245-254. [https://doi.org/10.1111/gwat.13265 doi: 10.1111/gwat.13265]&nbsp; [https://ngwa.onlinelibrary.wiley.com/doi/epdf/10.1111/gwat.13265 Free download from NGWA]</ref>.  
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*Low-Temperature Thermal Remediation: Gaining Traction as a Green Remedial Alternative. Horst, ''et al.'', 2018<ref name="HorstEtAl2018">Horst, J., Flanders, C., Klemmer, M., Randhawa, D.S., Rosso, D., 2018. Low-Temperature Thermal Remediation: Gaining Traction as a Green Remedial Alternative. Groundwater Monitoring and Remediation, 38(3), pp. 18-27. [https://doi.org/10.1111/gwmr.12295 doi: 10.1111/gwmr.12295]</ref>.
  
 
==Introduction==
 
==Introduction==
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[[File: Nagar1w2Fig1.png | thumb | 400px | Figure 1.  Water phase diagram showing the supercritical water region (not to scale).]]  
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[[File: MunhollandFig1.png | thumb | 500 px | Figure 1: Components and layout of a TISR<sup>®</sup> system]]
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Supercritical water oxidation (SCWO) is an [[Wikipedia: Advanced oxidation process | advanced oxidation process]] that holds enormous potential for the treatment of a wide range of organic wastes, in particular concentrated wet wastes in slurries such as biosolids, sludges, agricultural wastes, chemical wastes with recalcitrant chemicals such as [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)| perfluoroalkyl and polyfluoroalkyl substances (PFAS)]], and many more. SCWO relies on the unique reactivity and transport properties that occur when an aqueous waste stream is brought above the critical point of water (374&deg;C and 218 atm, or 704&deg;F and 3200 psi, see phase diagram in Figure 1). [[Wikipedia: Supercritical fluid | Supercritical water]] is a dense single phase with transport properties similar to those of a gas, and solvent properties comparable to those of a non-polar solvent<ref name="Tassaing2002">Tassaing, T., Danten, Y., and Besnard, M., 2002. Infrared spectroscopic study of hydrogen bonding in water at high temperature and pressure. Journal of Molecular Liquids, 101(1-3), pp. 149-158. [https://doi.org/10.1016/S0167-7322(02)00089-2 DOI: 10.1016/S0167-7322(02)00089-2]</ref>. Oxygen is fully soluble in supercritical water, resulting in extremely rapid and complete oxidation of all organics to carbon dioxide, clean water (that can be reused), and some non-leachable inorganic salts.  
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TISR<sup>®</sup> utilizes [[Wikipedia: Downhole heat exchanger | borehole heat exchangers (BHEs)]] to heat target treatment areas in the subsurface. This is achieved through a combination of solar collectors, which harness solar radiation as heat, and the utilization of other heat sources such as waste heat or hybrid heating with heat pumps. That heat is then transferred to the subsurface via a closed loop circulation system connected to the BHEs (Figure 1). By incorporating these additional heat sources, TISR<sup>®</sup> ensures a more robust and constant heat supply, enabling customization of the system to address specific site challenges and facilitate efficient heat transfer.
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The heating of the subsurface through TISR<sup>®</sup> accelerates various processes such as biodegradation, abiotic reactions, and contaminant desorption and dissolution. The technology is also suitable for diverse hydrogeologic environments, including sites with low permeability zones, due to the relatively uniform thermal conductivity of geologic materials, which is unaffected by grain size<ref name="MunhollandEtAl2024"/>. This versatility allows TISR<sup>®</sup> to integrate with conventional remediation technologies, enhancing their performance.
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One of the key advantages of TISR<sup>®</sup> is its ability to accelerate treatment processes while minimizing energy consumption. By harnessing renewable and sustainable energy sources such as solar radiation and effectively utilizing waste heat or hybrid heating with heat pumps, TISR<sup>®</sup> delivers an efficient, cost-effective remediation solution. Compatibility with multiple conventional remediation technologies makes it an effective option for addressing a variety of contamination challenges.
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==Scientific Principles==
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[[File: MunhollandFig2.png | thumb | 500 px | Figure 2: Effect of temperature on hydrolysis rates for VOCs]]
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During the TISR<sup>®</sup> heating process, thermal conduction and advection play a crucial role in boosting physical, biological, and chemical processes within the treatment zones, leading to enhanced attenuation, degradation, and removal of contaminants from the subsurface<ref>Dettmer, K., 2002. A Discussion of the Effects of Thermal Remediation Treatments on Microbial Degradation Processes. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, Technology Innovation Office, Washington, DC. [[Media: dettmer2002.pdf | free report]]&nbsp; [https://www.clu-in.org/download/techdrct/dettmer.pdf free download from clu-in.org]</ref><ref name="HorstEtAl2018"/>. TISR<sup>®</sup> systems are typically designed to enhance the biological activity and performance of other active technologies, such as [[Wikipedia: Air sparging | air sparge]]/[[Soil Vapor Extraction (SVE) | soil vapor extraction]] (AS/SVE) or [[Chemical Oxidation (In Situ - ISCO) | chemical oxidation]], by increasing the subsurface temperature by approximately 10°C to 20°C. The target groundwater temperature is often set to reach up to about 35°C, which is the optimal temperature for promoting the activity of mesophilic microbial communities responsible for biodegradation of certain contaminants. In cases where the objective is to maximize abiotic hydrolysis mechanisms, such as for some chlorinated alkanes, TISR<sup>®</sup> systems can be designed to reach a final groundwater temperature of up to 60°C.
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The effectiveness of TISR<sup>®</sup> in enhancing treatment performance has been demonstrated through several mechanisms, which are discussed below:
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 +
*Primary dechlorinating bacteria, such as [[Wikipedia: Dehalococcoides | Dehalococcoides]] and [[Wikipedia: Dehalogenimonas | Dehalogenimonas]], are known to be [[Wikipedia: Mesophile | mesophilic]]. Therefore, increasing the temperature can significantly enhance microbial activity and biodegradation by multiple orders of magnitude<ref>Macbeth, T., Truex, M., Powell, T., Michalsen, M., 2012. Combining Low-Energy Electrical Resistance Heating with Biotic and Abiotic Reactions for Treatment of Chlorinated Solvent DNAPL Source Areas. [https://serdp-estcp.mil/ Environmental Security Technology Certification Program (ESTCP)] [https://serdp-estcp.mil/projects/details/877a3b41-6bed-4f4a-b43a-87fbcd9b7f0b/er-200719-project-overview Project ER-200719 webpage]&nbsp; [[Media: Macbeth2012_ER-200719-FR.pdf | free download]]&nbsp; [https://www.youtube.com/watch?v=-EbwKbs8scE Project Summary Presentation]</ref>.
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*Reduced iron minerals, particularly iron sulfides, can participate in the abiotic degradation of chlorinated ethenes and other contaminants. The rates of these reactions generally depend on temperature, following the [[Wikipedia: Arrhenius equation | Arrhenius equation]].
  
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{| class="wikitable" style="float:left; margin-right:15px;"
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*[[Wikipedia: Hydrolysis | Hydrolysis]] rates for certain compounds exhibit high temperature dependence. For example, a 10°C increase can lead to a 50% reduction in the half-life of [[Wikipedia: 1,1,1-Trichloroethane | 1,1,1-trichloroethane (1,1,1-TCA)]]<ref>Suthersan, S., Horst, J., Klemmer, M., Malone, D., 2012. Temperature-Activated Auto-Decomposition Reactions: An Under-Utilized In Situ Remediation Solution. Groundwater Monitoring and Remediation, 32(3), pp. 34-40. [https://doi.org/10.1111/j.1745-6592.2012.01407.x doi: 10.1111/j.1745-6592.2012.01407.x]</ref>. Figure 2 presents the calculated temperature-dependent hydrolysis rates for 13 common [[Wikipedia: Volatile organic compound | volatile organic compounds (VOCs)]] at a pH of 7.
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|+ Table 1.  Comparison of SCWO with other thermal technologies
 
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! Technology
 
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! SCWO
 
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! SCWG
 
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! HTL/HTC
 
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! WAO
 
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|-
 
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| Temperature || >380&deg;C || >380&deg;C || 250-300&deg;C || 150-320&deg;C
 
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|-
 
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| Pressure || >240 bar || >240 bar || 40-200 bar || 10-200 bar
 
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|-
 
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| Oxidant || Required || None || None || Required
 
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|-
 
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| Reaction time || 2-10 sec. || 40-90 sec. || 30 min. to 2 hr.s || 30 min. to 3 hr.s
 
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|-
 
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| Corrosion potential || Moderate to high || Moderate || Low || Low to moderate
 
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|-
 
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| Risk of reactor plugging || Moderate to high || High || High || Low
 
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|-
 
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| Reaction || Exothermic || Endothermic || Endothermic || Exothermic
 
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|-
 
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| Useable products || CO<sub>2</sub> + clean H<sub>2</sub>O + heat + minerals || Syngas (H<sub>2</sub> + CH<sub>4</sub> + CO) || Biocrude/Biochar || Possible H<sub>2</sub>O, volatile fatty acids
 
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|-
 
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| By-products || None || Tars, phenols, recalcitrant N,</br>contaminated water || Tars, phenols, recalcitrant N,</br>contaminated water ||Tars, phenols, recalcitrant N,</br>contaminated water
 
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|-
 
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| Fate of feedstock N,</br>if any || N<sub>2</sub> gas || NH<sub>4</sub><sup>+</sup> in liquid effluent || NH<sub>4</sub><sup>+</sup> in liquid effluent +</br>N in (by)-products || NH<sub>4</sub><sup>+</sup> in liquid effluent +</br>N in (by)-products
 
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|-
 
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| colspan="5" style="background:white;" | Notes: SCWG = supercritical water gasification, HTL/HTC = [[Wikipedia: Hydrothermal liquefaction | hydrothermal liquefaction]]/carbonization, WAO = wet air oxidation
 
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|}
 
  
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For&nbsp;SCWO&nbsp;to&nbsp;be&nbsp;economical, the heat from the oxidation reaction is recovered and used in part to heat the influent stream, while the excess heat can be converted to electricity. Depending on the concentration of waste in the feedstock, SCWO reactors can be operated autothermally, i.e., no outside input of heat is required. Typical reaction times are in the order of 2-10 seconds, resulting in SCWO systems that are quite compact compared to other technologies (see Table 1). The process does not generate harmful by-products such as nitrogen oxides (NOx) or Sulfur oxides (SOx), carbon monoxide (CO), or odors<ref Name="Bermejo">Bermejo, M.D. and Cocero, M.J., 2006. Supercritical water oxidation: A technical review. AIChE Journal, 52(11) pp. 3933-3951. [https://doi.org/10.1002/aic.10993 DOI: 10.1002/aic.10993]</ref>. Typically, if present, ammonia and organic nitrogen in the waste undergoing treatment are converted to nitrogen gas, while phosphorous precipitates as phosphates and can be recovered. When [[Wikipedia: Halogen | halogen]] containing contaminants are treated (e.g., [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)| PFAS]]), halogen-carbon bonds are generally broken and [[Wikipedia: Halide | halide]] anions are released in solution (e.g., F- when treating PFAS or Cl- when treating [[Wikipedia: Trichloroethylene | trichloroethene (TCE)]] and [[Wikipedia: Tetrachloroethylene | tetrachloroethene (PCE)]]).
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*[[Wikipedia: Henry's law | Henry's Law]] constant, [[Wikipedia: Vapor pressure | vapor pressure]], solubility, and viscosity values are also temperature dependent. For instance, the Henry's Law constant values for many VOCs, including [[Wikipedia: Tetrachloroethylene | tetrachloroethene (PCE)]], have been observed to double between 8 and 24°C<ref>Chen, F., Freedman, D.L., Falta, R.W., Murdoch, L.C., 2012. Henry's law constants of chlorinated solvents at elevated temperatures. Chemosphere, 86(2), pp.156-165. [https://doi.org/10.1016/j.chemosphere.2011.10.004 doi: 10.1016/j.chemosphere.2011.10.004]</ref>.
  
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==Advantages and Disadvantages==
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*Rates of other processes that often limit the pace of remediation, such as dissolution, desorption, and [[Matrix Diffusion | back diffusion]], are positively correlated with temperature. This results in an enhanced bioavailability of contaminant mass that may otherwise be inaccessible.
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There are many advantages to SCWO treatment. SCWO is a destructive treatment in that the compounds treated are mineralized to simple elements or harmless molecules (e.g., water and carbon dioxide) rather than just being transferred to another medium. Another advantage is the absence of reaction by-products, incompletely oxidized contaminants or unreacted harmful oxidants (e.g., ozone). SCWO is an extremely rapid and effective reaction (typical reaction times are in the order of 5-10 seconds) making it possible to build systems that are very compact and have a high throughput. SCWO is also a very clean process. The highly oxidizing environment makes it possible to effectively treat all sorts of organic contaminants, often recalcitrant to other processes, with very high (>99%) destruction efficiencies. This includes treatment of trace contaminants, slurries of biosolids, waste oil, food wastes, plastics, or emerging contaminants such as PFAS or 1,4-dioxane. Also, the relatively moderate temperatures (380-600&deg;C) compared to other destructive technologies such as incineration, combined with the presence of supercritical water prevent the formation of NOx and SOx compounds. Lastly, SCWO treatment does not require drying of the waste, and both liquids and slurries can be treated using SCWO.  
 
  
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There are several disadvantages to SCWO treatment. First, a significant amount of energy needs to be expended to bring the oxidant and the waste undergoing treatment to the critical point of water. Although a large fraction of this energy can be efficiently recovered in heat exchangers, compensating for heat losses constrains SCWO to the treatment of concentrated wastes with sufficient organic content for the exothermic oxidation reaction to provide the necessary heat. Typically, a minimum calorific content of around 2 MJ/kg (which generally corresponds to a chemical oxygen demand of about 120-150 g/L) is needed for autothermal operation. For more dilute streams, external heating or supplementation of fuel (diesel, alcohol, waste oil, etc.) can be implemented, but it can rapidly become cost prohibitive. Thus, SCWO is currently not economical for very large volumes (>50,000 gallon/day) of very dilute waste streams. A second limitation is related to the pumping of the waste. Because the process is conducted at high pressure (240 bars or 3500 psi), positive displacement pumps are required. This limits SCWO to liquids and slurries that can be pumped. Waste streams that contain excessive grit or abrasive materials, and soils cannot currently be processed using SCWO.  
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These various mechanisms collectively contribute to the improved performance of other active treatments when temperature is moderately increased by utilization of TISR®.
  
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The many appealing benefits of supercritical water processing have stimulated engineers and entrepreneurs to invest significant efforts and resources in the development of the technology. Today, after roughly 30 years of development, commercial deployment is on the horizon<ref name="Marrone2013"/>. Technical challenges that have slowed down commercial deployment of SCWO are linked to the complex nature of a high-pressure, high-temperature process. Critical issues include reactor materials selection to resist corrosion (typically high nickel alloys are used), reactor designs and construction to withstand the corrosive nature of the reactive mass, dealing with highly exothermic reactions at high pressure and high temperature, plugging of the reactor by minerals deposits, and energy recovery for autothermal operation. Another challenge was the unrealistic goal of some companies entering the SCWO market to produce power from waste streams (often wastewater sludge) at a competitive cost (3-5 cents/kWh). This was not feasible with the available technology, which led to several business failures.  
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==Implementation and Practical Considerations==
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[[File: MunhollandFig3.png | thumb | 500 px | Figure 3: Transformation of 1,1-DCE and VC following installation of a TISR<sup>®</sup> system]]
 +
TISR<sup>®</sup> has proven successful in reducing contaminant concentrations across diverse hydrogeologic settings, including those with low and complex hydraulic conductivity conditions. Figure 3 shows a sharp initial decrease in [[Wikipedia: 1,1-Dichloroethylene | 1,1-dichloroethene (1,1-DCE)]] concentrations due to enhanced biodegradation, and then a temporary small increase followed by subsequent decreases in 1,1-DCE concentrations to below detection limits, possibly the result of temperature-enhanced desorption or dissolution of 1,1-DCE from the aquifer. There is also a temporary increase and then decrease in the concentrations of [[Wikipedia: Vinyl chloride | vinyl chloride (VC)]] (a biodegradation product) to very low levels.  
  
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The value proposition of treating recalcitrant wastes using SCWO is markedly different, especially in today’s context of increasing liability for trace levels of emerging contaminants such as PFAS. SCWO may prove to be the optimal treatment technology for many highly concentrated aqueous waste streams.
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The TISR<sup>®</sup> system construction utilizes off-the-shelf modular components, promoting cost-efficiency, reusability, and a reduced carbon footprint. Waste heat can supplement or replace the solar setup, and remote monitoring through dashboard apps reduces operation and maintenance costs. TISR® projects typically achieve an average capital cost payback within 1 to 3 years due to accelerated rates of remediation.
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[[File: Nagar1w2Fig2.png | thumb | 500px | Figure 2.  Duke SCWO pilot-scale system (during construction, thermal insulation removed). The system is housed in a standard 20 ft shipping container and can treat about 1 ton (or 270 gallons) of waste per day.]]
 
  
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==State of the Art==
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When implementing TISR<sup>®</sup>, [[Wikipedia: Solar irradiance | solar insolation]] and groundwater velocity must be considered for optimal equipment sizing and cycling. Depending on remedial goals and site history and conditions, the TISR<sup>®</sup> system and target temperatures may be designed to enhance specific remedial mechanisms (e.g. hydrolysis over bioremediation). Recently Ornelles ''et al.''<ref name="Ornelles"/> developed an easy to use Excel-based model that can be used to optimize TISR<sup>®</sup> design and predict subsurface temperature changes over time. Frequent monitoring of the temperature and microbial community composition relative to targets is useful for evaluating treatment effectiveness and optimizing system performance. The system and target temperatures can be customized to enhance specific remedial mechanisms based on site conditions and goals.  
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[[File: Nagar1w2Fig3.png | thumb |left| 400px | Figure 3.  Landfill leachate (left) and SCWO treated effluent (right). Effluent is odorless.]]  
 
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Relatively few large scale SCWO systems exist. Researchers at Duke University ([http://sanitation.pratt.duke.edu/community-treatment/about-community-treatment-project Deshusses lab]) have designed and built a prototype pilot-scale SCWO system housed in a standard 20-foot shipping container (Figure 2). This project was funded by the Reinvent the Toilet program of the [https://www.gatesfoundation.org/ Bill and Melinda Gates Foundation]. The pilot system is a continuous process designed to treat 1 ton of sludge per day at 10-20% dry solids content. The unit has been undergoing testing at Duke since early 2015. The design includes moderate preheating of the waste slurry, followed by mixing with supercritical water (~600&deg;C) and air, which serves as the oxidant. This internal mixing rapidly brings the waste undergoing treatment to supercritical conditions thereby minimizing corrosion and the risks of waste charring and associated reactor plugging. The organics in the sludge are rapidly oxidized to CO<sub>2</sub>, while the heat of oxidation is recovered to heat the influent waste. The reactor is a single tubular reactor. The high supercritical fluid velocity in the system helps with controlling mineral salts deposition in the reactor. The system is well instrumented, and operation is controlled using a supervisory control and data acquisition (SCADA) system with historian software for trends analysis and reporting of key performance indicators (e.g., temperatures and pressures, pollutant destruction). Experiments conducted with this pilot plant have shown effective treatment of a wide variety of otherwise problematic wastes such as primary, secondary and digested sludge slurries, landfill leachate (see Figure 3), animal waste, and co-contaminants including waste oil, food wastes, and plastics. The results are consistent with other SCWO studies and show very rapid treatment of all wastes with near complete conversion (often >99.9%) of organics to CO<sub>2</sub>. Total nitrogen and phosphorous removal are generally over 95% and 98%, respectively. Emerging contaminants such as pharmaceuticals, [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]], [[1,4-Dioxane | 1,4-dioxane]] and [[Wikipedia: Microplastics | microplastics]] are also treated with destruction generally exceeding 99%.
 
  
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Early projections for treatment costs (Capital Expenditures + Operating Expenditures) for slurries are in the range of $12 to $90 per ton (or $0.04 to $0.37 per gallon) depending on system scale and contaminant concentration, with a majority of the cost coming from amortizing the equipment. These cost projections make SCWO treatment very competitive compared to other treatment technologies for high-strength wastes. When treating large volumes of water, combining SCWO with another technology (e.g., nanofiltration, reverse osmosis, or adsorption onto GAC) should be considered so that only the concentrated brines or spent sorbent are treated using SCWO, thereby increasing the cost effectiveness of the overall treatment.
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==Summary==
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{| class="wikitable" style="float:right; margin-left:15px;"
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TISR<sup>®</sup> is a cost-effective and adaptable technology that can be customized to address specific site challenges. It can be used as a standalone solution or be integrated with existing remediation strategies to enhance their effectiveness. TISR<sup>®</sup> is particularly effective in challenging hydrogeological conditions and can be optimized to suit specific treatment mechanisms. By shortening the active remediation timeframe, TISR<sup>®</sup> reduces lifecycle costs and minimizes the carbon footprint associated with the remediation process.
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|+ Table 2.  Results for influent biosolids and treated effluent using Duke University SCWO pilot-scale plant
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<br clear="right"/>
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|-
 
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! Substance
 
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! Residual</br>(ng/L)
 
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! Removal
 
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|-
 
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| PFBA || 10.20 || 99.86%
 
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|-
 
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| PFHxA || 5.15 || 99.89%
 
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|-
 
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| PFNA || 1.07 || 99.90%
 
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|-
 
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| PFDA || 0.80 || 99.97%
 
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|-
 
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| PFUnA || <1.10 || >99.89%
 
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|-
 
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| PFBS || <0.19|| >99.98%
 
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|-
 
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| PFPes || <0.29 || >99.98%
 
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|-
 
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| PFHxS || 0.28 || 99.99%
 
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|-
 
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| PFOS || 0.65 || 99.99%
 
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|-
 
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| colspan="3" style="background:white;" | Note: Similar destruction efficiencies were obtained when treating AFFF solutions.
 
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|}
 
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==SCWO for the Treatment of PFAS and AFFF==
 
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Several reports have indicated that PFAS can be treated using SCWO<ref name="Kucharzyk2017">Kucharzyk, K.H., Darlington, R., Benotti, M., Deeb, R. and Hawley, E., 2017. Novel treatment technologies for PFAS compounds: A critical review. Journal of Environmental Management, 204(2), pp. 757-764.  [https://doi.org/10.1016/j.jenvman.2017.08.016 DOI: 10.1016/j.jenvman.2017.08.016]&nbsp;&nbsp; Manuscript available from: [https://www.researchgate.net/profile/Katarzyna_kate_Kucharzyk/publication/319125507_Novel_treatment_technologies_for_PFAS_compounds_A_critical_review/links/5a06590b4585157013a3be77/Novel-treatment-technologies-for-PFAS-compounds-A-critical-review.pdf ResearchGate]</ref>. Several runs treating biosolids known to contain PFAS as well as dilutions of pure [[Wikipedia: Firefighting foam | aqueous film forming foam (AFFF)]] have also been conducted with the Duke SCWO system. Typical results are shown in Table 2. They indicate very effective treatment performance, with for example 110,000 ng/L PFOS in the feed reduced to 0.79 ng/L in the effluent, and many other PFAS reduced to below their detection limits. No HF was found in the effluent gas, and all the fluorine from the destroyed PFAS was accounted for as fluoride in the effluent water. These results show the ability of the SCWO process to destroy PFAS to levels well below the EPA health advisory levels of 70 ng/L for PFOS and PFOA. The [https://www.serdp-estcp.org/ Environmental Security Technology Certification Program (ESTCP)] project number [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/ER20-5350/ER20-5350 ER20-5350]<ref name="Deshusses2020">Deshusses, M.A., 2020. Supercritical Water Oxidation (SCWO) for Complete PFAS Destruction. Environmental Security Technology Certification Program (ESTCP) Project number ER20-5350. [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/ER20-5350/ER20-5350 Project website]</ref> launched in June 2020 will assess the technical feasibility of using supercritical water oxidation (SCWO) for the complete destruction of PFAS in a variety of relevant waste streams and will evaluate the cost effectiveness of the treatment.
 
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[https://vimeo.com/1019489395 TISR<sup>®</sup> Explanation Video]

Latest revision as of 19:44, 13 October 2026

Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes

Thermal In Situ Sustainable Remediation (TISR®; US Pat. Nos. 10,384,246 and 10,688,545) is a cost-effective and adaptable low temperature thermal remediation technology that accelerates contaminant treatment. It achieves this by enhancing biotic and abiotic contaminant degradation rates through a modest increase in subsurface temperature. TISR® is suitable for a wide range of hydrogeologic settings. It also offers reduced operational costs, a lower carbon footprint, and possibly shorter remedial timeframes than more conventional methods.

Related Article(s):

Contributors: Jonah Munholland, Julia Vidonish, and Craig Divine

Key Resources:

  • Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes, Final Report. ESTCP Project ER20-5028[1].
  • Advances in Low-Temperature Thermal Remediation. Munholland et al., 2024[2].
  • A Design Tool for Solar Thermal Remediation Using Borehole Heat Exchangers. Ornelles, Falta, and Divine, 2023[3].
  • Low-Temperature Thermal Remediation: Gaining Traction as a Green Remedial Alternative. Horst, et al., 2018[4].

Introduction

File:MunhollandFig1.png
Figure 1: Components and layout of a TISR® system

TISR® utilizes borehole heat exchangers (BHEs) to heat target treatment areas in the subsurface. This is achieved through a combination of solar collectors, which harness solar radiation as heat, and the utilization of other heat sources such as waste heat or hybrid heating with heat pumps. That heat is then transferred to the subsurface via a closed loop circulation system connected to the BHEs (Figure 1). By incorporating these additional heat sources, TISR® ensures a more robust and constant heat supply, enabling customization of the system to address specific site challenges and facilitate efficient heat transfer.

The heating of the subsurface through TISR® accelerates various processes such as biodegradation, abiotic reactions, and contaminant desorption and dissolution. The technology is also suitable for diverse hydrogeologic environments, including sites with low permeability zones, due to the relatively uniform thermal conductivity of geologic materials, which is unaffected by grain size[2]. This versatility allows TISR® to integrate with conventional remediation technologies, enhancing their performance.

One of the key advantages of TISR® is its ability to accelerate treatment processes while minimizing energy consumption. By harnessing renewable and sustainable energy sources such as solar radiation and effectively utilizing waste heat or hybrid heating with heat pumps, TISR® delivers an efficient, cost-effective remediation solution. Compatibility with multiple conventional remediation technologies makes it an effective option for addressing a variety of contamination challenges.

Scientific Principles

File:MunhollandFig2.png
Figure 2: Effect of temperature on hydrolysis rates for VOCs

During the TISR® heating process, thermal conduction and advection play a crucial role in boosting physical, biological, and chemical processes within the treatment zones, leading to enhanced attenuation, degradation, and removal of contaminants from the subsurface[5][4]. TISR® systems are typically designed to enhance the biological activity and performance of other active technologies, such as air sparge/ soil vapor extraction (AS/SVE) or chemical oxidation, by increasing the subsurface temperature by approximately 10°C to 20°C. The target groundwater temperature is often set to reach up to about 35°C, which is the optimal temperature for promoting the activity of mesophilic microbial communities responsible for biodegradation of certain contaminants. In cases where the objective is to maximize abiotic hydrolysis mechanisms, such as for some chlorinated alkanes, TISR® systems can be designed to reach a final groundwater temperature of up to 60°C.

The effectiveness of TISR® in enhancing treatment performance has been demonstrated through several mechanisms, which are discussed below:

  • Primary dechlorinating bacteria, such as Dehalococcoides and Dehalogenimonas, are known to be mesophilic. Therefore, increasing the temperature can significantly enhance microbial activity and biodegradation by multiple orders of magnitude[6].
  • Reduced iron minerals, particularly iron sulfides, can participate in the abiotic degradation of chlorinated ethenes and other contaminants. The rates of these reactions generally depend on temperature, following the Arrhenius equation.
  • Rates of other processes that often limit the pace of remediation, such as dissolution, desorption, and back diffusion, are positively correlated with temperature. This results in an enhanced bioavailability of contaminant mass that may otherwise be inaccessible.

These various mechanisms collectively contribute to the improved performance of other active treatments when temperature is moderately increased by utilization of TISR®.

Implementation and Practical Considerations

File:MunhollandFig3.png
Figure 3: Transformation of 1,1-DCE and VC following installation of a TISR® system

TISR® has proven successful in reducing contaminant concentrations across diverse hydrogeologic settings, including those with low and complex hydraulic conductivity conditions. Figure 3 shows a sharp initial decrease in 1,1-dichloroethene (1,1-DCE) concentrations due to enhanced biodegradation, and then a temporary small increase followed by subsequent decreases in 1,1-DCE concentrations to below detection limits, possibly the result of temperature-enhanced desorption or dissolution of 1,1-DCE from the aquifer. There is also a temporary increase and then decrease in the concentrations of vinyl chloride (VC) (a biodegradation product) to very low levels.

The TISR® system construction utilizes off-the-shelf modular components, promoting cost-efficiency, reusability, and a reduced carbon footprint. Waste heat can supplement or replace the solar setup, and remote monitoring through dashboard apps reduces operation and maintenance costs. TISR® projects typically achieve an average capital cost payback within 1 to 3 years due to accelerated rates of remediation.

When implementing TISR®, solar insolation and groundwater velocity must be considered for optimal equipment sizing and cycling. Depending on remedial goals and site history and conditions, the TISR® system and target temperatures may be designed to enhance specific remedial mechanisms (e.g. hydrolysis over bioremediation). Recently Ornelles et al.[3] developed an easy to use Excel-based model that can be used to optimize TISR® design and predict subsurface temperature changes over time. Frequent monitoring of the temperature and microbial community composition relative to targets is useful for evaluating treatment effectiveness and optimizing system performance. The system and target temperatures can be customized to enhance specific remedial mechanisms based on site conditions and goals.

Summary

TISR® is a cost-effective and adaptable technology that can be customized to address specific site challenges. It can be used as a standalone solution or be integrated with existing remediation strategies to enhance their effectiveness. TISR® is particularly effective in challenging hydrogeological conditions and can be optimized to suit specific treatment mechanisms. By shortening the active remediation timeframe, TISR® reduces lifecycle costs and minimizes the carbon footprint associated with the remediation process.

References

  1. ^ Divine, C., Munholland, J., Zardouzian, E., Justicia-Leon, S., Aspinall, J.V., Randhawa, D., Falta, R., Freedman, D., Becker, M., 2025. Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes, Final Report. Environmental Security Technology Certification Program (ESTCP), Project ER20-5028. Project Website  Final Report.pdf
  2. ^ 2.0 2.1 Munholland, J, Rosso, D., Randhawa, D., Devine, C., Pennington, A., 2024. Advances in Low-Temperature Thermal Remediation. In: García-Rincón, J., Gatsios, E., Lenhard, R.J., Atekwana, E.A., Naidu, R. (eds), Advances in the Characterisation and Remediation of Sites Contaminated with Petroleum Hydrocarbons, Chapter 18 pp. 623-653. Environmental Contamination Remediation and Management series, Springer Nature. doi: 10.1007/978-3-031-34447-3_18  Open Access Chapter
  3. ^ 3.0 3.1 Ornelles, A.D., Falta, R.W., Divine, C.E., 2023. A Design Tool for Solar Thermal Remediation Using Borehole Heat Exchangers. Ground Water, 61(2), pp. 245-254. doi: 10.1111/gwat.13265  Free download from NGWA
  4. ^ 4.0 4.1 Horst, J., Flanders, C., Klemmer, M., Randhawa, D.S., Rosso, D., 2018. Low-Temperature Thermal Remediation: Gaining Traction as a Green Remedial Alternative. Groundwater Monitoring and Remediation, 38(3), pp. 18-27. doi: 10.1111/gwmr.12295
  5. ^ Dettmer, K., 2002. A Discussion of the Effects of Thermal Remediation Treatments on Microbial Degradation Processes. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, Technology Innovation Office, Washington, DC. free report  free download from clu-in.org
  6. ^ Macbeth, T., Truex, M., Powell, T., Michalsen, M., 2012. Combining Low-Energy Electrical Resistance Heating with Biotic and Abiotic Reactions for Treatment of Chlorinated Solvent DNAPL Source Areas. Environmental Security Technology Certification Program (ESTCP) Project ER-200719 webpage  free download  Project Summary Presentation
  7. ^ Suthersan, S., Horst, J., Klemmer, M., Malone, D., 2012. Temperature-Activated Auto-Decomposition Reactions: An Under-Utilized In Situ Remediation Solution. Groundwater Monitoring and Remediation, 32(3), pp. 34-40. doi: 10.1111/j.1745-6592.2012.01407.x
  8. ^ Chen, F., Freedman, D.L., Falta, R.W., Murdoch, L.C., 2012. Henry's law constants of chlorinated solvents at elevated temperatures. Chemosphere, 86(2), pp.156-165. doi: 10.1016/j.chemosphere.2011.10.004

See Also

TISR® Explanation Video