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A Conceptual Site Model (CSM) is a collection of information about a contaminated site that integrates the available evidence regarding its hydrogeologic setting, contaminant sources, exposure pathways, potential receptors, and site history. A CSM for a [[Wikipedia: Light non-aqueous phase liquid | Light Non-Aqueous Phase Liquid (LNAPL)]] site focuses on several key concepts:  the stage in the LNAPL site life cycle, LNAPL distribution in the subsurface and the resulting mobility of the LNAPL, LNAPL as a source of dissolved and vapor plumes, and the attenuation of LNAPL sources over time.
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==Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes==
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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>
  
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'''Related Article(s)'''
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'''Related Article(s):'''
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* [[LNAPL Remediation Technologies]]
 
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* [[NAPL Mobility]]
 
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* [[Natural Source Zone Depletion (NSZD)]]
 
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* [[Natural Attenuation in Source Zone and Groundwater Plume - Bemidji Crude Oil Spill]]
 
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* [[Monitored Natural Attenuation (MNA)]]
 
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* [[Biodegradation - Hydrocarbons]]
 
  
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'''CONTRIBUTOR(S):''' [[Dr. Charles Newell, P.E. | Charles Newell]]
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*[[Thermal Remediation]]
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*[[Thermal Remediation - Electrical Resistance Heating | Electrical Resistance Heating]]
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*[[Thermal Conduction Heating (TCH)]]
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*[[Thermal Remediation - Combined Remedies | Combined Remedies]]
  
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'''Key Resource(s):'''
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'''Contributors:''' Jonah Munholland, Julia Vidonish, and Craig Divine
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* LNAPL Site Management: LCSM Evolution, Decision Process, and Remedial Technologies. LNAPL-3. ITRC.<ref name="LNAPL-3">Interstate Technology and Regulatory Council (ITRC), 2018. LNAPL Site Management: LCSM Evolution, Decision Process, and Remedial Technologies. LNAPL-3. ITRC, LNAPL Update Team, Washington, DC.  [https://lnapl-3.itrcweb.org LNAPL-3 Website]</ref>
 
  
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* Managing Risk at LNAPL Sites - Frequently Asked Questions, 2nd Edition. API.<ref name="Sale2018"> Sale, T., Hopkins, H., and Kirkman, A., 2018. Managing Risk at LNAPL Sites - Frequently Asked Questions, 2nd Edition. American Petroleum Institute (API), Washington, DC. 72 pages. [https://www.api.org/oil-and-natural-gas/environment/clean-water/ground-water/lnapl/lnapl-faqs Free download from API.] [https://www.enviro.wiki/index.php?title=File:Sale-2018_LNAPL_FAQs_2nd_ed.pdf Report.pdf]</ref>
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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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==Life Cycle of LNAPL Sites==
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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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[[File:Newell1w2Fig1.png |thumb|left|250px| Figure 1. Early, Middle, and Late Stage LNAPL releases<ref name= "Sale2018"/>. The key distinctions are the presence of continuous LNAPL that can be mobile and the amount of time that has elapsed for NSZD to remove LNAPL.]]
 
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A Conceptual Site Model (CSM) is a collection of information about a contaminated site that integrates the available evidence regarding its hydrogeologic setting, contaminant sources, exposure pathways, potential receptors, and site history (see ASTM E1689-95(2014)<ref name="ASTM2014a"> ASTM, 2014. Standard Guide for Developing Conceptual Site Models for Contaminated Sites. ASTM E1689-95(2014), ASTM International, West Conshohocken, PA. [https://doi.org/10.1520/E1689-95R14 DOI: 10.1520/E1689-95R14]  http://www.astm.org/cgi-bin/resolver.cgi?E1689</ref> and ASTM E2531-06(2014)<ref name="ASTM2014b"> ASTM, 2014. Standard Guide for Development of Conceptual Site Models and Remediation Strategies for Light Nonaqueous-Phase Liquids Released to the Subsurface. ASTM E2531-06(2014), ASTM International, West Conshohocken, PA. [https://doi.org/10.1520/E2531-06R14  DOI: 10.1520/E2531-06R14] http://www.astm.org/cgi-bin/resolver.cgi?E2531</ref>).  When developing a CSM for an LNAPL site, it is important to understand that LNAPL releases evolve and change from what are referred to as Early Stage sites to Middle Stage and then to Late Stage sites<ref name="Sale2018"/> (Figure 1).
 
  
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An Early Stage site is characterized by the presence of a continuous LNAPL zone where a thick layer of LNAPL accumulation (also known as free product) is observed in monitoring wells. The continuous LNAPL zone (or LNAPL body) may be mobile at Early Stage sites, migrating into previously non-impacted areas. Removal of significant LNAPL mass by active pumping may be feasible at these sites. Early Stage sites are now relatively rare in the United States due to stringent environmental regulations enacted in the 1980s which emphasized preventing releases.
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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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[[File:Newell1w2Fig2a.png |thumb|500px| Figure 2a.  Time lapse conceptualization of the formation of an LNAPL body<ref name="ITRC2019"> Interstate Technology and Regulatory Council (ITRC), 2019. LNAPL Training: Connecting the Science to Managing Sites. Part 1: Understanding LNAPL Behavior in the Subsurface. ITRC, Washington, DC. [[Media: ITRC2019_LNAPLtrainingPart1.pdf | Slides.pdf]]</ref>.]]
 
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[[File:Newell1w2Fig2b.png |thumb|500px| Figure 2b. Sand tank experiment of an LNAPL release<ref name="ITRC2019"/>.]]
 
  
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Many sites in the U.S. are now considered to be in the Middle Stage, where the LNAPL thickness in wells has been largely depleted by natural spreading of the LNAPL body, [[Natural Source Zone Depletion (NSZD)]], smearing of the water table, and/or active remediation, and where the LNAPL bodies are stable or shrinking<ref name="LNAPL-3"/><ref name="Sale2018"/> (Figure 1). Active pumping characteristically only recovers LNAPL at relatively low rates of under 100 gallons per acre per year at Middle Stage sites, but NSZD rates may be much higher, on the order of 100s to 1,000s of gallons per acre per year. Middle Stage dissolved phase plumes, typically comprised of monoaromatics such as benzene, toluene, ethyl benzene, and xylenes, are stable or shrinking over time.
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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>.
  
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Late Stage sites only have a sparse distribution of residual (trapped) LNAPL due to long-term NSZD and any active remediation that has been performed at the site. The potential risks to receptors are typically low at Late Stage sites due to relatively low concentrations of LNAPL constituents in the dissolved phase and/or vapor plumes.
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==Introduction==
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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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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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==LNAPL Body Formation==
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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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LNAPLs released from tanks, pits, pipelines, or other sources will percolate downwards under the influence of gravity through permeable pathways in the unsaturated zone (e.g., soil pore space, fractures, and macropores) depending on the volume and pressure head of the LNAPL release, until encountering an impermeable layer or the water table, causing the LNAPL body to spread laterally.  The Interstate Technology and Regulatory Council (ITRC)<ref name="LNAPL-3"/> describes this downward movement toward the water table this way:
 
  
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<blockquote>''During the downward movement of LNAPL through the soil, the presence of confining layers, subsurface heterogeneities, or other preferential pathways may result in irregular and complex lateral spreading and/or perching of LNAPL before the water table is encountered. Once at the water table, the LNAPL will spread laterally in a radial fashion as well as penetrate vertically downward into the saturated zone, displacing water to some depth proportional to the driving force of the vertical LNAPL column (or LNAPL head). The vertical penetration of LNAPL into the saturated zone will continue to occur as long as the downward force produced by the LNAPL head or pressure from the LNAPL release exceeds the counteracting forces produced by the resistance of the soil matrix and the buoyancy resulting from the density difference between LNAPL and groundwater.''<ref name="LNAPL-3"/></blockquote>
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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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While the release at the surface is still active, the LNAPL body can expand until the LNAPL addition rate is equal to the NSZD depletion rate.  However, once the release at the surface is stopped, the expansion will stop relatively quickly, and the LNAPL body will stabilize. Figure 2a shows a conceptual depiction of this release scenario and Figure 2b shows a sand tank experiment of an LNAPL release. Because of the buoyancy effects, LNAPL releases that reach the water table will form LNAPL bodies that “like icebergs, are partially above and below the water table”.<ref name="Sale2018"/>
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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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==Key Implications of the LNAPL Conceptual Site Model==
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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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The nature of multi-phase flow processes in porous media (e.g., the interaction of LNAPL, water, and air in the pore spaces of an unconsolidated aquifer) has several important implications for environmental professionals in areas including interpretation of LNAPL thickness in monitoring wells and assessment of the long-term risk associated with LNAPL source zones.  A few of the key implications are described below.
 
  
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===Three States of LNAPL===
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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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LNAPL can be found in the subsurface in three different states:
 
  
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# '''Residual LNAPL''' is trapped and immobile but can undergo composition and phase changes and generate dissolved hydrocarbon plumes in saturated zones and/or vapors in unsaturated zones. The fraction of the total pore space occupied by this discontinuous LNAPL is referred to as the residual saturation, with other phases such as water and air in the remainder of the pore space.
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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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# '''Mobile LNAPL''' is LNAPL at greater than the residual saturation. Mobile LNAPL can accumulate in a well and is potentially recoverable, but is not migrating (i.e., the LNAPL body is not expanding).
 
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# '''Migrating LNAPL''' is LNAPL at greater than the residual concentration which is observed to expand into previously non-impacted locations over time (e.g., LNAPL appears in a monitoring well that had previously been clean).
 
  
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These three LNAPL states can cause different concerns and in some cases require different remediation goals.  
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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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===LNAPL “Apparent Thickness” is a Poor Metric for Risk Management===
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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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[[File:Newell1w2Fig3.png |thumb|left|600px| Figure 3. Five LNAPL Thickness Scenarios for five different physical settings<ref name="Sale2018"/>.]]
 
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[[File:Newell1w2Fig4.png |thumb|350px| Figure 4.  Apparent LNAPL thickness versus LNAPL transmissivity, showing no correlation<ref name="Hawthorne2015">Hawthorne, J.M., 2015.  Nationwide (USA) Statistical Analysis of LNAPL Transmissivity, in: R. Darlington and A.C. Barton (Chairs), Bioremediation and Sustainable Environmental Technologies—2015. Third International Symposium on Bioremediation and Sustainable Environmental Technologies (Miami, FL), page C-017, Battelle Memorial Institute, Columbus, OH. www.battelle.org/biosymp  [[Media:Hawthorne2015.pdf | Abstract.pdf]]</ref>.]]
 
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LNAPL thickness in monitoring wells is often referred to as the “apparent LNAPL thickness” because at first glance this LNAPL thickness might be expected to be the thickness of LNAPL that is in the formation, but in reality it is not well correlated with the thickness of the LNAPL zone in the subsurface for several reasons.
 
  
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First, different physical settings can produce different LNAPL thicknesses in monitoring wells.  Sale et al. (2018) show five different scenarios that produce very different responses with regard to apparent LNAPL thickness (Figure 3).  Scenario A shows an LNAPL apparent thickness in the monitoring well that is at static equilibrium with LNAPL in an unconfined aquifer.  Scenario B, while also an unconfined aquifer, is comprised of very fine-grained soils that cause the LNAPL thickness in the well to be much higher than in Scenario A.  In Scenario C, the LNAPL has accumulated under a confined unit (likely due to an underground release of LNAPL below the confining unit), and the LNAPL has risen above the groundwater potentiometric surface, leading to a large (and misleading) LNAPL thickness in the monitoring well.  Scenario D, LNAPL in a perched unit, also shows a very different response from the other scenarios. Scenario E, LNAPL in fractured system, shows that the LNAPL can penetrate below the water table, and that LNAPL thickness in a well is dependent on the pressure from accumulation of LNAPL in the fractures<ref name="Sale2018"/>.
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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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Second, apparent LNAPL thickness is affected by changes in the groundwater surface elevation (or water table).  Generally, when groundwater elevations are higher than typical, the LNAPL thickness in monitoring wells will decrease or go to zero because the groundwater will redistribute any mobile LNAPL into what previously was the unsaturated zone.  During lower groundwater elevation periods, much more of the LNAPL will occur as a continuous phase near the water table, leading to higher LNAPL thicknesses in wells.
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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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Overall, LNAPL thickness measurements are useful for delineating the extent of mobile LNAPL in the saturated zone and can provide useful data for understanding the vertical distribution of LNAPL in the formation<ref name="Hawthorne2011">Hawthorne, J.M., 2011. Diagnostic Gauge Plots—Simple Yet Powerful LCSM Tools. Applied NAPL Science Review (ANSR), 1(2). [http://naplansr.com/diagnostic-gauge-plots-volume-1-issue-2-february-2011/ Website] [[Media:Hawthorne2011.pdf | Report.pdf]]</ref><ref name="Kirkman2013">Kirkman, A.J., Adamski, M., and Hawthorne, M., 2013. Identification and Assessment of Confined and Perched LNAPL Conditions. Groundwater Monitoring and Remediation, 33 (1), pp. 75–86. [https://doi.org/10.1111/j.1745-6592.2012.01412.x  DOI:10.1111/j.1745-6592.2012.01412.x]</ref>. But LNAPL thickness by itself is a very poor indicator of the feasibility of LNAPL recovery<ref name="LNAPL-2">Interstate Technology and Regulatory Council (ITRC), 2009. Evaluating LNAPL Remedial Technologies for Achieving Project Goals. LNAPL-2. ITRC, LNAPLs Team, Washington, DC. www.itrcweb.org  [[Media:ITRC-LNAPL-2.pdf | Report.pdf]]</ref><ref name="Hawthorne2015"/> (see [[NAPL Mobility]]) (Figure 4).  Because there is little correlation between apparent LNAPL thickness and LNAPL mobility, there is also little correlation between apparent thickness and the risk to receptors from the LNAPL.
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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]]
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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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===Complete LNAPL Remediation Is Very Challenging===
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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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Sale et al. (2018) described the problems with attaining complete LNAPL remediation this way:
 
  
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<blockquote>''Experience of the last few decades has taught us: 1) our best efforts often leave some LNAPL in place, and 2) the remaining LNAPL often sustains exceedances of drinking water standards in release areas for extended periods. Entrapment of LNAPLs at residual saturations is a primary factor constraining our success. Other challenges include the low solubility of LNAPL, the complexity of the subsurface geologic environment, access limitations associated with surface structures, and concentration goals that are often three to five orders of magnitude less than typical initial concentrations within LNAPL zones.''<ref name="Sale2018"/></blockquote>
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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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In particular, the discontinuous residual LNAPL cannot be removed (or recovered) by pumping, and ''in situ'' remediation is expensive and not completely effective (see [[LNAPL Remediation Technologies]]).  However, many regulatory programs require “LNAPL recovery to the extent practicable.”  The lack of quantitative metrics and the lack of correlation between apparent LNAPL thicknesses and subsurface LNAPL makes this a problematic requirement in many cases and the ITRC (2018) cautions “Thickness or concentration data alone may not provide a sound basis for defining the point at which a cleanup objective is achieved.”<ref name="LNAPL-3"/>  However, Sale et al. (2018) describe metrics such as LNAPL transmissivity, limited/infrequent well thicknesses, decline curve analysis, asymptotic analysis, and comparison to NSZD rates that can be used to determine when LNAPL has been removed the extent practicable<ref name="Sale2018"/>.
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==Summary==
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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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===Attenuation Processes are Active and Important===
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<br clear="right"/>
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Both LNAPL source zones and their dissolved phase hydrocarbon plumes are attenuated by biodegradation and other attenuation process.  In the source zone, this attenuation is called [[Natural Source Zone Depletion (NSZD)]] (see also [[Natural Attenuation in Source Zone and Groundwater Plume - Bemidji Crude Oil Spill]]).  In the dissolved plume it is called [[Monitored Natural Attenuation (MNA)]] (see also  [[Biodegradation - Hydrocarbons]]).  These processes generally limit the length of dissolved phase hydrocarbon plumes to a few hundred feet<ref name="Newell1998">Newell, C.J., and Connor, J.A., 1998. Characteristics of Dissolved Hydrocarbon Plumes: Results from Four Studies, Version 1.1. American Petroleum Institute, Soil/Groundwater Technical Task Force, Washington, DC. [https://www.enviro.wiki/index.php?title=File:Newell-1998-chararacterization_of_dissolved_Pet._Hydro_Plumes.pdf  Report.pdf]</ref> via processes that have been well known and understood since the mid-1990s.
 
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However, NSZD is “by far, the biggest new idea for LNAPLs in the last decade.”<ref name="Sale2018"/>  Originally, LNAPL bodies were thought to attenuate very slowly via dissolution and volatilization.  In 2006, it was discovered that NSZD rates are orders of magnitude higher than originally thought, largely due to direct biodegradation of LNAPL constituents to methane and carbon dioxide by methanogenic consortiums of naturally occurring bacteria<ref name="Lundegard2006">Lundegard, P.D., and Johnson, P.C., 2006. Source Zone Natural Attenuation at Petroleum Spill Sites—II: Application to a Former Oil Field. Groundwater Monitoring and Remediation. 26(4), pp. 93-106.  [ https://doi.org/10.1111/j.1745-6592.2006.00115.x  DOI: 10.1111/j.1745-6592.2006.00115.x]</ref><ref name="Garg2017">Garg, S., Newell, C., Kulkarni, P., King, D., Adamson, D.T., Irianni Renno, M., and Sale, T., 2017. Overview of Natural Source Zone Depletion: Processes, Controlling Factors, and Composition Change. Groundwater Monitoring and Remediation, 37(3), pp. 62-81.  [https://doi.org/10.1111/gwmr.12219 DOI:  10.1111/gwmr.12219] [[Media:Garg2017gwmr.12219.pdf | Report.pdf]]</ref>.  NSZD processes play an important role in risk mitigation and the long-term stability of LNAPL bodies<ref name="Mahler2012">
 
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Mahler, N., Sale, T., and Lyverse, M., 2012. A Mass Balance Approach to Resolving LNAPL Stability. Groundwater, 50(6), pp 861-871.  [https://doi.org/10.1111/j.1745-6584.2012.00949.x DOI: 10.1111/j.1745-6584.2012.00949.x]</ref><ref name="LNAPL-3"/>.
 
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===Risk from LNAPL Source Zones Diminishes Over Time===
 
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At Early Stage LNAPL sites, the expansion of the LNAPL body is a risk that needs to be addressed.  Fortunately, this type of site is relatively rare. For Middle and Late Stage sites, the primary risks are associated with phase changes (dissolution of the LNAPL forming a dissolved plume and volatilization from the LNAPL or dissolved plume forming hydrocarbon vapors).  As described above, MNA can often control the dissolved phase (see [[Monitored Natural Attenuation (MNA) of Fuels]]), while aerobic biodegradation in the unsaturated zone greatly reduces the vapor intrusion risk from hydrocarbon vapors (see [[Vapor Intrusion - Separation Distances from Petroleum Sources]]).
 
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Understanding LNAPL body mobility and stability is important to understand the potential risks posed by LNAPL.  The relative magnitude of LNAPL mobility can be determined by measuring the LNAPL transmissivity (see [[NAPL Mobility]]).  If the transmissivity is below a threshold level (in the range of 0.1 to 0.8 ft<sup>2</sup>/day) then the LNAPL likely cannot be recovered efficiently by pumping, but above this transmissivity level recovery is feasible<ref name="LNAPL-3"/>.  Michigan’s LNAPL guidance states “if the NAPL has a transmissivity greater than 0.5 ft<sup>2</sup>/day, it is likely that the NAPL can be recovered in a cost-effective and efficient manner unless a demonstration is made to show otherwise.”  Kansas LNAPL guidance requires “recovery of all LNAPL with a transmissivity greater than 0.8 ft<sup>2</sup>/day that can be recovered in an efficient, cost-effective manner.”<ref name="LNAPL-3"/>.  The stability of the entire LNAPL body can be evaluated using statistical tools to determine if migration of LNAPL is occurring<ref name="Hawthorne2013">Hawthorne, J.M., Stone, C.D., Helsel, D., 2013. LNAPL Body Stability Part 2: Daughter Plume Stability via Spatial Moments Analysis. Applied NAPL Science Review (ANSR), 3(5).  [http://naplansr.com/lnapl-body-stability-part-2-daughter-plume-stability-via-spatial-moments-analysis-volume-3-issue-5-september-2013/ Website] [[Media:Hawthorne2013.pdf | Report.pdf]]</ref>.
 
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==Overview of Modern LNAPL Conceptual Site Model==
 
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[[File:Newell1w2Fig5.png |thumb|500px| Figure 5.  A higher tier of LNAPL CSM is useful as LNAPL site complexity increases<ref name="LNAPL-3"/>.]]
 
−
The ITRC (2018) describes the typical evolution of an LCSM over the course of the remediation process which can be broken into three separate stages:
 
−
* An ''Initial LCSM'' focuses on identifying the LNAPL concerns, such as a risk to health or safety, any LNAPL migration, LNAPL-specific regulations, and physical or aesthetic impacts.  
 
−
* A ''Remedy Selection LCSM'' supports remedial technology evaluation by characterizing aspects of the LNAPL and site subsurface that may impact remedial technology performance.
 
−
* A ''Design and Performance LCSM'' focuses on presenting the technical information needed to establish remediation objectives, design and implement remedies or control measures, and track progress toward defined remediation endpoints.
 
−
 
 
−
One key question when developing an LCSM is “how much data is enough.”  In general, the answer is that the existing data is sufficient for the current stage of the remediation project when it allows the stakeholders to agree on a path forward<ref name="LNAPL-3"/>.  Figure 5 shows that as the level of complexity of a site increases, a higher tier of LCSM is useful to provide enough information for making decisions<ref name="LNAPL-3"/><ref name="ASTM2014a"/>.  The higher tier of information could be higher data density, additional tools for a given line of evidence, or other evaluations.
 
−
 
 
−
==LNAPL Concerns, Remediation Goals and Objectives==
 
−
Finally, the ITRC (2018) provides a methodology for identifying LNAPL concerns, verifying those concerns, selecting LNAPL remediation goals, and determining LNAPL remediation objectives.  Examples of each of these concepts are provided below:
 
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* '''Potential Concerns:'''  Human or ecological risk concerns, fire or explosivity issues, LNAPL migration, LNAPL-specific regulatory concerns, other concerns such as odors or geotechnical issues.
 
−
* '''Verifying Concerns:'''  Measure LNAPL transmissivity to determine if it is recoverable; measure vertical and horizontal separation distances between buildings and LNAPL bodies to screen for vapor intrusion concerns.
 
−
* '''Remediation Goals:'''  Reduce mobile LNAPL saturation, abate unacceptable soil concentrations, terminate LNAPL body migration, abate unacceptable constituent concentrations in dissolved and vapor phases.
 
−
* '''Remediation Objectives:'''  Recover LNAPL to the extent practicable based on transmissivity, reduce soil concentrations to below regulatory limits, stop LNAPL migration with a barrier, contain migrating groundwater plume (if present), reduce groundwater and vapor concentration to acceptable levels.
 
−
* '''Remediation Technologies:'''  LNAPL Mass Recovery technologies, LNAPL phase change technologies, LNAPL Mass Control technologies, combinations of technologies.
 
−
 
 
−
Overall, a LNAPL Conceptual Site Model that integrates key site specific information and current technical knowledge about LNAPL sites in general is instrumental to successful site management, where LNAPL concerns drive remediation goals, goals drive remediation objectives, and the objectives form the basis for the selection of remediation technologies.
 
  
 
==References==
 
==References==
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+
<references />
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<references/>
 
  
 
==See Also==
 
==See Also==
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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

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