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==Estimating PCE/TCE Abiotic First-Order Reductive Dechlorination Rate Constants in Clayey Soils Under Anoxic Conditions==  
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==Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes==  
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The U.S. Department of Defense (DoD) faces many challenges in restoring aquifers at contaminated sites, often due to back-diffusion of tetrachloroethene (PCE) and trichloroethene (TCE) from low-permeability clay zones. The uptake, storage, and subsequent long-term release of these dissolved contaminants from clays are key processes in understanding the longevity, intensity, and risks associated with many persistent chlorinated ethene groundwater plumes. Although naturally occurring abiotic and biotic dechlorination processes in clays may reduce stored contaminant mass and significantly aid natural attenuation, no standardized field method currently exists to verify or quantify these reactions. It is critical to remediation design efforts to demonstrate and validate a cost-effective in situ approach for assessing these dechlorination processes using first-order rate constants. An approach was developed and applied across eight DoD sites to support Remedial Project Managers (RPMs) and regulators in evaluating natural attenuation potential in clay-rich environments.
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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.
 
<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):'''
  
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*[[Monitored Natural Attenuation (MNA)]]
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*[[Thermal Remediation]]
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*[[Monitored Natural Attenuation (MNA) of Chlorinated Solvents]]
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*[[Thermal Remediation - Electrical Resistance Heating | Electrical Resistance Heating]]
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*[[Monitored Natural Attenuation - Transitioning from Active Remedies]]
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*[[Thermal Conduction Heating (TCH)]]
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*[[Matrix Diffusion]]
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*[[Thermal Remediation - Combined Remedies | Combined Remedies]]
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*[[REMChlor - MD]]
 
  
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'''Contributors:''' Dani Tran, Dr. Charles Schaefer, Dr. Charles Werth
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'''Contributors:''' Jonah Munholland, Julia Vidonish, and Craig Divine
  
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'''Key Resource:'''
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'''Key Resources:'''
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*Schaefer, C.E, Tran, D., Nguyen, D., Latta, D.E., Werth, C.J., 2025. Evaluating Mineral and In Situ Indicators of Abiotic Dechlorination in Clayey Soils (3)
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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>.
 +
 
 +
*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>.
 +
 
 +
*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>.
 +
 
 +
*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==
−
Cost-effective methods are needed to verify the occurrence of natural dechlorination processes and quantify their dechlorination rates in clays under ambient in situ conditions in order to reliably predict their long-term influence on plume longevity and mass discharge. However, accurately determining these rates is challenging due to slow reaction kinetics, the transient nature of transformation products, and the interplay of biotic and abiotic mechanisms within the clay matrix or at clay-sand interfaces. Tools capable of quantifying these reactions and assessing their role in mitigating plume persistence would be a significant aid for long-term site management.
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[[File: MunhollandFig1.png | thumb | 500 px | Figure 1: Components and layout of a TISR<sup>®</sup> system]]
 +
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.
 +
 
 +
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.
 +
 
 +
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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For reductive abiotic dechlorination under anoxic conditions, a 1% hydrochloric acid (HCl) extraction of a sample of native clay coupled with X-ray diffraction (XRD) data can be used as a screening level tool to estimate reductive dechlorination rate constants. These rate constants can be inserted into fate and transport models such as [[REMChlor - MD]]<ref>Falta, R., and Wang, W., 2017. A semi-analytical method for simulating matrix diffusion in numerical transport models. Journal of Contaminant Hydrology, 197, pp. 39-49. [https://doi.org/10.1016/j.jconhyd.2016.12.007 doi: 10.1016/j.jconhyd.2016.12.007]&nbsp; [[Media: FaltaWang2017.pdf | Open Access Manuscript]]</ref><ref>Kulkarni, P.R., Adamson, D.T., Popovic, J., Newell, C.J., 2022. Modeling a well-charactized perfluorooctane sulfate (PFOS) source and plume using the REMChlor-MD model to account for matrix diffusion. Journal of Contaminant Hydrology, 247, Article 103986. [https://doi.org/10.1016/j.jconhyd.2022.103986 doi: 10.1016/j.jconhyd.2022.103986]&nbsp; [[Media: KulkarniEtAl2022.pdf | Open Access Manuscript]]</ref> to quantify abiotic dechlorination impacts within clay aquitards on chlorinated solvent plumes. Thus, determination of the abiotic reductive dechlorination rate constant for a particular clayey soil can be readily utilized to provide a more accurate assessment of aquifer cleanup timeframes for groundwater plumes that are being sustained by contaminant back-diffusion.
+
==Scientific Principles==
 +
[[File: MunhollandFig2.png | thumb | 500 px | Figure 2: Effect of temperature on hydrolysis rates for VOCs]]
 +
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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==Recommended Approach==
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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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[[File: TranFig1.pdf | thumb | 600 px | Figure 1: First-order rate constants for abiotic reductive dechlorination of TCE under anaerobic conditions. Circles are data from Schaefer ''et al.'', 2021<ref>Schaefer, C.E., Ho, P., Berns, E., Werth, C., 2021. Abiotic dechlorination in the presence of ferrous minerals. Journal of Contaminant Hydrology, 241, 103839. [https://doi.org/10.1016/j.jconhyd.2021.103839 doi: 10.1016/j.jconhyd.2021.103839]&nbsp; [[Media: SchaeferEtAl2021.pdf | Open Access Manuscript]]</ref>, filled squares from Schaefer ''et al.'', 2018<ref name="SchaeferEtAl2018"/>, and  Schaefer ''et al.'', 2017<ref>Schaefer, C.E., Ho., Gurr, C., Berns, E., Werth, C., 2017. Abiotic dechlorination of chlorinated ethenes in natural clayey soils: impacts of mineralogy and temperature. Journal of Contaminant Hydrology, 206, pp. 10-17. [https://doi.org/10.1016/j.jconhyd.2017.09.007 doi: 10.1016/j.jconhyd.2017.09.007]&nbsp; [[Media: SchaeferEtAl2017.pdf | Open Access Manuscript]]</ref>, and open squares from Schaefer ''et al.'', 2025<ref name="SchaeferEtAl2025"/>. ]]
 
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[[File: TranFig2.png | thumb | 600 px | Figure 2: Flowchart diagram of field screening procedures]]
 
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The recommended approach builds upon the methodology and findings of a recent study<ref name="SchaeferEtAl2025">Schaefer, C.E., Tran, D., Nguyen, D., Latta, D.E., Werth, C.J., 2025. Evaluating Mineral and In Situ Indicators of Abiotic Dechlorination in Clayey Soils. Groundwater Monitoring and Remediation, 45(2), pp. 31-39. [https://doi.org/10.1111/gwmr.12709 doi: 10.1111/gwmr.12709]</ref>, emphasizing field-based and analytical techniques to quantify abiotic first-order reductive dechlorination rate constants for PCE and TCE in clayey soils under anoxic conditions. Key components of this evaluation are listed below:
 
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#<u>Zone Identification:</u> The focus of the investigation should be to delineate clayey zones adjacent to hydraulically conductive zones.
 
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#<u>Ferrous Mineral Quantification:</u> Assess ferrous mineral context in clay via 1% HCl extraction at ambient temperature over a 10-minute interval.
 
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#<u>Mineralogical Characterization:</u> Conduct XRD analysis with the specific intent of identifying the presence of pyrite and biotite.
 
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#<u>Reduced Gas Analysis:</u> Measurement of reduced gases such as acetylene, ethene, and ethane concentrations in clay samples. Gas-tight sampling devices (e.g., En Core® soil samplers by En Novative Technologies, Inc.)  should be used to ensure sample integrity during collection and transport. 
 
  
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Clay samples should be collected within a few centimeters of the high-permeability interface, with optional additional sampling further inward. For mineralogical analysis, a defined interval may be collected and subsequently subsampled. To preserve sample integrity, exposure to air should be minimized during collection, transport, and handling. Homogenization should occur within an anaerobic chamber, and if subsamples are required for external analysis, they must be shipped in gas-tight, anaerobic containers.
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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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Estimation of the abiotic reductive first-order rate constant for PCE and TCE is based on the “reactive” ferrous content in the clay. Reactive ferrous content (Fe(II)<sub>r</sub>) is estimated as shown in Equation 1:
+
*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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::'''Equation 1:'''&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; <big>''Fe(II)<sub><small>r</small></sub> = DA + XRD<sub><small>pyr</small></sub> - XRD<sub><small>biotite</small></sub>''</big>
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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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where ''DA'' is the ferrous content from the dilute acid (1% HCl) extraction, ''XRD<sub><small>pyr</small></sub>'' is the pyrite content from XRD analysis, and ''XRD<sub><small>biotite</small></sub>'' is the biotite content from XRD analysis<ref name="SchaeferEtAl2025"/>.
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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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Abiotic dechlorination is unlikely to contribute to mitigating contaminant back-diffusion when reactive ferrous iron (Fe(II)<sub><small>r</small></sub>) concentrations are below 100 mg/kg (Figure 1). For Fe(II)<sub><small>r</small></sub> above 100 mg/kg, the first-order rate constant for PCE and TCE reductive dechlorination can be estimated using the correlation shown in Figure 1<ref name="SchaeferEtAl2018">Schaefer, C.E., Ho, P., Berns, E., Werth, C., 2018. Mechanisms for abiotic dechlorination of trichloroethene by ferrous minerals under oxic and anoxic conditions in natural sediments. Environmental Science and Technology, 52(23), pp.13747-13755. [https://doi.org/10.1021/acs.est.8b04108 doi: 10.1021/acs.est.8b04108]</ref><ref>Borden, R.C., Cha, K.Y., 2021. Evaluating the impact of back diffusion on groundwater cleanup time. Journal of Contaminant Hydrology, 243, Article 103889. [https://doi.org/10.1016/j.jconhyd.2021.103889 doi: 10.1016/j.jconhyd.2021]&nbsp; [[Media: BordenCha2021.pdf | Open Access Manuscript]]</ref>. The rate constant exhibits a strong positive correlation with the logarithm of reactive Fe(II) content (Pearson’s ''r'' = 0.82), with a slope of 4.7 × 10⁻⁸ L g⁻¹ d⁻¹ (log mg kg⁻¹)⁻¹.
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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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Figure 2 presents a decision flowchart designed to evaluate the significance and extent of abiotic reductive dechlorination. By applying Equation 1 to the dilute acid extractable Fe(II) plus measured mineral species data from clay samples, the reactive ferrous iron content (Fe(II)<sub><small>r</small></sub>) can be quantified, enabling a streamlined assessment of the extent to which abiotic processes are contributing to the mitigation of contaminant back-diffusion.
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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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If Fe(II)r is ≥ 100 mg/kg, a first-order dechlorination rate constant can be estimated and subsequently used within a contaminant fate and transport model. However, if acetylene is detected in the clay, even with Fe(II)r less than 100 mg/kg, then bench-scale testing using methods similar to those described in a recent study<ref name="SchaeferEtAl2025"/> is recommended, as such results would likely be inconsistent with those shown in Figure 1, suggesting some other mechanism might be involved, or that the system mineralogy might be more complex than anticipated. Even if Fe(II)r ≥ 100 mg/kg, confirmatory bench-scale testing may be conducted for additional verification and to refine estimation of the abiotic dechlorination rate constant.
+
==Implementation and Practical Considerations==
 +
[[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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==Summary and Recommendations==
+
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.
−
The approach outlined above is intended to serve as a generalized guide for practitioners and site managers to cost-effectively determine the extent to which beneficial abiotic reductive dechlorination reactions are likely occurring in low permeability (e.g., clayey) zones. This approach may be contraindicated if co-contaminants are present. It is currently unclear whether other classes of potentially reactive chemicals, such as trinitrotoluene (TNT) or chlorinated ethanes, could interact competitively with PCE and TCE.  
 
  
−
In addition, it remains unclear how other classes of compounds such as per- and polyfluoroalkyl substances (PFAS) may interact or sorb with ferrous minerals and potentially inhibit abiotic dechlorination reactions. Coupling these recommended activities with conventional site investigation tasks would provide an opportunity to perform many of the up-front screening activities with minimal additional project costs. It is important to note that the guidance proposed herein pertains to particularly low permeability media. Sites with complex or varying lithology, where the mineralogy and/or redox conditions may vary, might require evaluation of multiple samples to provide appropriate site-wide information.
+
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.  
  
 +
==Summary==
 +
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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==See Also==
 
==See Also==
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*[https://serdp-estcp.mil/projects/details/a7e3f7b5-ed82-4591-adaa-6196ff33dd60 ESTCP Project ER20-5031 – In Situ Verification and Quantification of Naturally Occurring Dechlorination Rates in Clays: Demonstrating Processes that Mitigate Back-Diffusion and Plume Persistence]
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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