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==OPTically-based In-situ Characterization System (OPTICS)==  
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==Thermal In Situ Sustainable Remediation to Enhance Biotic and Abiotic Reactions and Accelerate Remediation Timeframes==  
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OPTICS combines robust aquatic instrumentation and innovative data processing techniques to measure concentrations of a wide range of dissolved and particulate chemical contaminants in surface water at unprecedented scales. OPTICS is used for a variety of environmental applications including remedial investigation, conceptual site model validation, baseline characterization, source control evaluation, plume characterization, and remedial monitoring.
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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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<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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*[[Contaminated Sediments - Introduction]]
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*[[Thermal Remediation]]
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*[[Characterization, Assessment & Monitoring]]
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*[[Thermal Remediation - Electrical Resistance Heating | Electrical Resistance Heating]]
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*[[Mercury in Sediments]]
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*[[Thermal Conduction Heating (TCH)]]
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*[[Thermal Remediation - Combined Remedies | Combined Remedies]]
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'''Contributors:''' Jonah Munholland, Julia Vidonish, and Craig Divine
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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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'''Contributor(s):'''
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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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*Grace Chang, Ph.D.
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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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*Todd Martin, P.E.
 
  
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'''Key Resource(s):'''
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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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*Optically based quantification of fluxes of mercury, methyl mercury, and polychlorinated biphenyls (PCBs) at Berry’s Creek tidal estuary, New Jersey<ref name="ChangEtAl2019">Chang, G., Martin, T., Whitehead, K., Jones, C., Spada, F., 2019. Optically based quantification of fluxes of mercury, methyl mercury, and polychlorinated biphenyls (PCBs) at Berry’s Creek tidal estuary, New Jersey. Limnology and Oceanography, 64(1), pp. 93-108. [https://doi.org/10.1002/lno.11021 doi: 10.1002/lno.11021]&nbsp;&nbsp; [[Media: ChangEtAl2019.pdf | Open Access Article]]</ref>
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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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*OPTically-based In-situ Characterization System (OPTICS) to quantify concentrations of mass fluxes of mercury and methylmercury in South River, Virginia, USA<ref name="ChangEtAl2018">Chang, G., Martin, T., Spada, F., Sackmann, B., Jones, C., Whitehead, K., 2018. OPTically-based In-situ Characterization System (OPTICS) to quantify concentrations and mass fluxes of mercury and methylmercury in South River, Virginia, USA. River Research and Applications, 34(9), pp.  1132-1141. [https://doi.org/10.1002/rra.3361 doi: 10.1002/rra.3361]</ref>
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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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*Evaluation of stormwater as a potential source of polychlorinated biphenyls (PCBs) to Pearl Harbor, Hawaii<ref name="ChangEtAl2024">Chang, G., Spada, F., Brodock, K., Hutchings, C., Markillie, K., 2024. Evaluation of stormwater as a potential source of polychlorinated biphenyls (PCBs) to Pearl Harbor, Hawaii. Case Studies in Chemical and Environmental Engineering, 9, Article 100659. [https://doi.org/10.1016/j.cscee.2024.100659 doi: 10.1016/j.cscee.2024.100659]&nbsp;&nbsp; [[Media: ChangEtAl2024.pdf | Open Access Article]]</ref>
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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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==Background==
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==Scientific Principles==
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[[File:ChangFig2.png | thumb | 400px| Figure 1. Example of instrumentation used for OPTICS monitoring.]]
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[[File: MunhollandFig2.png | thumb | 500 px | Figure 2: Effect of temperature on hydrolysis rates for VOCs]]
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[[File:ChangFig1.png | thumb | 400px| Figure 2. Schematic diagram illustrating the OPTICS methodology. High resolution in-situ data are integrated with traditional discrete sample analytical data using partial least-square regression to derive high resolution chemical contaminant concentration data series.]]
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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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Nationwide, the liability due to contaminated sediments is estimated in the trillions of dollars. Stakeholders are assessing and developing remedial strategies for contaminated sediment sites in major harbors and waterways throughout the U.S. The mobility of contaminants in surface water is a primary transport and risk mechanism<ref>Thibodeaux, L.J., 1996. Environmental Chemodynamics: Movement of Chemicals in Air, Water, and Soil, 2nd Edition, Volume 110 of Environmental Science and Technology: A Wiley-Interscience Series of Texts and Monographs. John Wiley & Sons, Inc. 624 pages. ISBN: 0-471-61295-2</ref><ref>United States Environmental Protection Agency (USEPA), 2005. Contaminated Sediment Remediation Guidance for Hazardous Waste Sites. Office of Superfund Remediation and Technology Innovation Report, EPA-540-R-05-012. [[Media: 2005-USEPA-Contaminated_Sediment_Remediation_Guidance.pdf | Report.pdf]]</ref><ref>Lick, W., 2008. Sediment and Contaminant Transport in Surface Waters. CRC Press. 416 pages. [https://doi.org/10.1201/9781420059885 doi:  10.1201/9781420059885]</ref>; therefore, long-term monitoring of both particulate- and dissolved-phase contaminant concentration prior to, during, and following remedial action is necessary to document remedy effectiveness. Source control and total maximum daily load (TMDL) actions generally require costly manual monitoring of dissolved and particulate contaminant concentrations in surface water. The magnitude of cost for these actions is a strong motivation to implement efficient methods for long-term source control and remedial monitoring.  
 
  
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Traditional surface water monitoring requires mobilization of field teams to manually collect discrete water samples, send samples to laboratories, and await laboratory analysis so that a site evaluation can be conducted. These traditional methods are well known to have inherent cost and safety concerns and are of limited use (due to safety concerns and standby requirements for resources) in capturing the effects of episodic events (e.g., storms) that are important to consider in site risk assessment and remedy selection. Automated water samplers are commercially available but still require significant field support and costly laboratory analysis. Further, automated samplers may not be suitable for analytes with short hold-times and temperature requirements.
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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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Optically-based characterization of surface water contaminants is a cost-effective alternative to traditional discrete water sampling methods. Unlike discrete water sampling, which typically results in sparse data at low resolution, and therefore, is of limited use in determining mass loading, OPTICS (OPTically-based In-situ Characterization System) provides continuous data and allows for a complete understanding of water quality and contaminant transport in response to natural processes and human impacts<ref name="ChangEtAl2019"/><ref name="ChangEtAl2018"/><ref name="ChangEtAl2024"/><ref>Bergamaschi, B.A., Fleck, J.A., Downing, B.D., Boss, E., Pellerin, B., Ganju, N.K., Schoellhamer, D.H., Byington, A.A., Heim, W.A., Stephenson, M., Fujii, R., 2011. Methyl mercury dynamics in a tidal wetland quantified using in situ optical measurements. Limnology and Oceanography, 56(4), pp. 1355-1371. [https://doi.org/10.4319/lo.2011.56.4.1355 doi: 10.4319/lo.2011.56.4.1355]&nbsp;&nbsp; [[Media: BergamaschiEtAl2011.pdf | Open Access Article]]</ref><ref>Bergamaschi, B.A., Fleck, J.A., Downing, B.D., Boss, E., Pellerin, B.A., Ganju, N.K., Schoellhamer, D.H., Byington, A.A., Heim, W.A., Stephenson, M., Fujii, R., 2012. Mercury Dynamics in a San Francisco Estuary Tidal Wetland: Assessing Dynamics Using In Situ Measurements. Estuaries and Coasts, 35, pp. 1036-1048. [https://doi.org/10.1007/s12237-012-9501-3 doi: 10.1007/s12237-012-9501-3]&nbsp;&nbsp; [[Media: BergamaschiEtAl2012a.pdf | Open Access Article]]</ref><ref>Bergamaschi, B.A., Krabbenhoft, D.P., Aiken, G.R., Patino, E., Rumbold, D.G., Orem, W.H., 2012. Tidally driven export of dissolved organic carbon, total mercury, and methylmercury from a mangrove-dominated estuary. Environmental Science and Technology, 46(3), pp. 1371-1378. [https://doi.org/10.1021/es2029137 doi: 10.1021/es2029137]&nbsp;&nbsp; [[Media: BergamaschiEtAl2012b.pdf | Open Access Article]]</ref>. The OPTICS tool integrates commercial off-the-shelf ''in situ'' aquatic sensors (Figure 1), periodic discrete surface water sample collection, and a multi-parameter statistical prediction model<ref name="deJong1993">de Jong, S., 1993. SIMPLS: an alternative approach to partial least squares regression. Chemometrics and Intelligent Laboratory Systems, 18(3), pp. 251-263. [https://doi.org/10.1016/0169-7439(93)85002-X doi: 10.1016/0169-7439(93)85002-X]</ref><ref name="RosipalKramer2006">Rosipal, R. and Krämer, N., 2006. Overview and Recent Advances in Partial Least Squares, In: Subspace, Latent Structure, and Feature Selection: Statistical and Optimization Perspectives Workshop, Revised Selected Papers (Lecture Notes in Computer Science, Volume 3940), Springer-Verlag, Berlin, Germany. pp. 34-51. [https://doi.org/10.1007/11752790_2 doi: 10.1007/11752790_2]</ref> to provide high temporal and/or spatial resolution characterization of surface water chemicals of potential concern (COPCs) (Figure 2).
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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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==Technology Overview==
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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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The principle behind OPTICS is based on the relationship between optical properties of natural waters and the particles and dissolved material contained within them<ref>Boss, E. and Pegau, W.S., 2001. Relationship of light scattering at an angle in the backward direction to the backscattering coefficient. Applied Optics, 40(30), pp. 5503-5507. [https://doi.org/10.1364/AO.40.005503 doi: 10.1364/AO.40.005503]</ref><ref>Boss, E., Twardowski, M.S., Herring, S., 2001. Shape of the particulate beam spectrum and its inversion to obtain the shape of the particle size distribution. Applied Optics, 40(27), pp. 4884-4893. [https://doi.org/10.1364/AO.40.004885 doi:10/1364/AO.40.004885]</ref><ref>Babin, M., Morel, A., Fournier-Sicre, V., Fell, F., Stramski, D., 2003. Light scattering properties of marine particles in coastal and open ocean waters as related to the particle mass concentration. Limnology and Oceanography, 48(2), pp. 843-859. [https://doi.org/10.4319/lo.2003.48.2.0843 doi: 10.4319/lo.2003.48.2.0843]&nbsp;&nbsp; [[Media: BabinEtAl2003.pdf | Open Access Article]]</ref><ref>Coble, P., Hu, C., Gould, R., Chang, G., Wood, M., 2004. Colored dissolved organic matter in the coastal ocean: An optical tool for coastal zone environmental assessment and management. Oceanography, 17(2), pp. 50-59. [https://doi.org/10.5670/oceanog.2004.47 doi: 10.5670/oceanog.2004.47]&nbsp;&nbsp; [[Media: CobleEtAl2004.pdf | Open Access Article]]</ref><ref>Sullivan, J.M., Twardowski, M.S., Donaghay, P.L., Freeman, S.A., 2005. Use of optical scattering to discriminate particle types in coastal waters. Applied Optics, 44(9), pp. 1667–1680. [https://doi.org/10.1364/AO.44.001667 doi: 10.1364/AO.44.001667]</ref><ref>Twardowski, M.S., Boss, E., Macdonald, J.B., Pegau, W.S., Barnard, A.H., Zaneveld, J.R.V., 2001. A model for estimating bulk refractive index from the optical backscattering ratio and the implications for understanding particle composition in case I and case II waters. Journal of Geophysical Research: Oceans, 106(C7), pp. 14,129-14,142. [https://doi.org/10.1029/2000JC000404 doi: 10/1029/2000JC000404]&nbsp;&nbsp; [[Media: TwardowskiEtAl2001.pdf | Open Access Article]]</ref><ref>Chang, G.C., Barnard, A.H., McLean, S., Egli, P.J., Moore, C., Zaneveld, J.R.V., Dickey, T.D., Hanson, A., 2006. In situ optical variability and relationships in the Santa Barbara Channel: implications for remote sensing. Applied Optics, 45(15), pp. 3593–3604. [https://doi.org/10.1364/AO.45.003593 doi: 10.1364/AO.45.003593]</ref><ref>Slade, W.H. and Boss, E., 2015. Spectral attenuation and backscattering as indicators of average particle size. Applied Optics, 54(24), pp. 7264-7277. [https://doi.org/10.1364/AO.54.007264 doi: 10/1364/AO.54.007264]&nbsp;&nbsp; [[Media: SladeBoss2015.pdf | Open Access Article]]</ref>. Surface water COPCs such as heavy metals and polychlorinated biphenyls (PCBs) are hydrophobic in nature and tend to sorb to materials in the water column, which have unique optical signatures that can be measured at high-resolution using ''in situ'', commercially available aquatic sensors<ref>Agrawal, Y.C. and Pottsmith, H.C., 2000. Instruments for particle size and settling velocity observations in sediment transport. Marine Geology, 168(1-4), pp. 89-114. [https://doi.org/10.1016/S0025-3227(00)00044-X doi: 10.1016/S0025-3227(00)00044-X]</ref><ref>Boss, E., Pegau, W.S., Gardner, W.D., Zaneveld, J.R.V., Barnard, A.H., Twardowski, M.S., Chang, G.C., Dickey, T.D., 2001. Spectral particulate attenuation and particle size distribution in the bottom boundary layer of a continental shelf. Journal of Geophysical Research: Oceans, 106(C5), pp. 9509-9516. [https://doi.org/10.1029/2000JC900077  doi: 10.1029/2000JC900077]&nbsp;&nbsp; [[Media: BossEtAl2001.pdf | Open Access Article]]</ref><ref>Boss, E., Pegau, W.S., Lee, M., Twardowski, M., Shybanov, E., Korotaev, G. Baratange, F., 2004. Particulate backscattering ratio at LEO 15 and its use to study particle composition and distribution. Journal of Geophysical Research: Oceans, 109(C1), Article C01014. [https://doi.org/10.1029/2002JC001514 doi: 10.1029/2002JC001514]&nbsp;&nbsp; [[Media: BossEtAl2004.pdf | Open Access Article]]</ref><ref>Briggs, N.T., Slade, W.H., Boss, E., Perry, M.J., 2013. Method for estimating mean particle size from high-frequency fluctuations in beam attenuation or scattering measurement. Applied Optics, 52(27), pp. 6710-6725. [https://doi.org/10.1364/AO.52.006710 doi: 10.1364/AO.52.006710]&nbsp;&nbsp; [[Media: BriggsEtAl2013.pdf | Open Access Article]]</ref>. Therefore, high-resolution concentrations of COPCs can be accurately and robustly derived from ''in situ'' measurements using statistical methods.
 
  
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The OPTICS method is analogous to the commonly used empirical derivation of total suspended solids concentration (TSS) from optical turbidity using linear regression<ref>Rasmussen, P.P., Gray, J.R., Glysson, G.D., Ziegler, A.C., 2009. Guidelines and procedures for computing time-series suspended-sediment concentrations and loads from in-stream turbidity-sensor and streamflow data. In: Techniques and Methods, Book 3: Applications of Hydraulics, Section C: Sediment and Erosion Techniques, Ch. 4. 52 pages. U.S. Geological Survey.&nbsp;&nbsp; [[Media: RasmussenEtAl2009.pdf | Open Access Article]]</ref>. However, rather than deriving one response variable (TSS) from one predictor variable (turbidity), OPTICS involves derivation of one response variable (e.g., PCB concentration) from a suite of predictor variables (e.g., turbidity, temperature, salinity, and fluorescence of chlorophyll-a) using multi-parameter statistical regression. OPTICS is based on statistical correlation – similar to the turbidity-to-TSS regression technique. The method does not rely on interpolation or extrapolation.  
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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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The OPTICS technique utilizes partial least-squares (PLS) regression to determine a combination of physical, optical, and water quality properties that best predicts chemical contaminant concentrations with high variance. PLS regression is a statistically based method combining multiple linear regression and principal component analysis (PCA), where multiple linear regression finds a combination of predictors that best fit a response and PCA finds combinations of predictors with large variance<ref name="deJong1993"/><ref name="RosipalKramer2006"/>. Therefore, PLS identifies combinations of multi-collinear predictors (''in situ'', high-resolution physical, optical, and water quality measurements) that have large covariance with the response values (discrete surface water chemical contaminant concentration data from samples that are collected periodically, coincident with ''in situ'' measurements). PLS combines information about the variances of both the predictors and the responses, while also considering the correlations among them. PLS therefore provides a model with reliable predictive power.
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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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OPTICS ''in situ'' measurement parameters include, but are not limited to current velocity, conductivity, temperature, depth, turbidity, dissolved oxygen, and fluorescence of chlorophyll-a and dissolved organic matter. Instrumentation for these measurements is commercially available, robust, deployable in a wide variety of configurations (e.g., moored, vessel-mounted, etc.), powered by batteries, and records data internally and/or transmits data in real-time. The physical, optical, and water quality instrumentation is compact and self-contained. The modularity and automated nature of the OPTICS measurement system enables robust, long-term, autonomous data collection for near-continuous monitoring.  
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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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[[File:ChangFig3.png | thumb | 400px| Figure 3. OPTICS to characterize COPC variability in the context of site processes at BCSA. (A) Tidal oscillations (Elev.<sub>MSL</sub>) and precipitation (Precip.). (B) – (D) OPTICS-derived particulate mercury (PHg) and methylmercury (PMeHg) and total PCBs (TPCBs). Open circles represent discrete water sample data.]] OPTICS measurements are provided at a significantly reduced cost relative to traditional monitoring techniques used within the environmental industry. Cost performance analysis shows that monitoring costs are reduced by more than 85% while significantly increasing the temporal and spatial resolution of sampling. The reduced cost of monitoring makes this technology suitable for a number of environmental applications including, but not limited to site baseline characterization, source control evaluation, dredge or stormflow plume characterization, and remedy performance monitoring. OPTICS has been successfully demonstrated for characterizing a wide variety of COPCs: mercury, methylmercury, copper, lead, PCBs, dichlorodiphenyltrichloroethane (DDT) and its related compounds (collectively, DDX), and 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD or dioxin) in a number of different environmental systems ranging from inland lakes and rivers to the coastal ocean. To date, OPTICS has been limited to surface water applications. Additional applications (e.g., groundwater) would require further research and development.
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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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==Applications==
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==Implementation and Practical Considerations==
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[[File:ChangFig4.png | thumb | 400px| Figure 4. OPTICS reveals baseflow daily cycling and confirms storm-induced particle-bound COPC resuspension and mobilization through bank interaction. (A) Flow rate (Q) and precipitation (Precip). (B) – (C) OPTICS-derived particulate mercury (PHg) and methylmercury (PMeHg). Open circles represent discrete water sample data.]]
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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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[[File:ChangFig5.png | thumb | 400px| Figure 5. Three-dimensional volume plot of high spatial resolution OPTICS-derived PCBs in exceedance of baseline showing that PCBs were discharged from the outfall (yellow arrow), remained in suspension, and dispersed elsewhere before settling.]]  
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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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An OPTICS study was conducted at Berry’s Creek Study Area (BCSA), New Jersey in 2014 and 2015 to understand COPC sources and transport mechanisms for development of an effective remediation plan. OPTICS successfully extended periodic discrete surface water samples to continuous, high-resolution measurements of PCBs, mercury, and methylmercury to elucidate COPC sources and transport throughout the BCSA tidal estuary system. OPTICS provided data at resolution sufficient to investigate COC variability in the context of physical processes. The results (Figure 3) facilitated focused and effective site remediation and management decisions that could not be determined based on periodic discrete samples alone, despite over seven years of monitoring at different locations throughout the system over a range of different seasons, tidal phases, and environmental conditions. The BCSA OPTICS methodology and its results have undergone official peer review overseen by the U.S. Environmental Protection Agency (USEPA), and those results have been published in peer-reviewed literature<ref name="ChangEtAl2019"/>.  
 
  
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OPTICS was applied at the South River, Virginia in 2016 to quantify sources of legacy mercury in the system that are contributing to recontamination and continued elevated mercury concentrations in fish tissue. OPTICS provided information necessary to identify mechanisms for COPC redistribution and to quantify the relative contribution of each mechanism to total mass transport of mercury and methylmercury in the system. Continuous, high-resolution COPC data afforded by OPTICS helped resolve baseflow daily cycling that had never before been observed at the South River (Figure 4) and provided data at temporal resolution necessary to verify storm-induced particle-bound COC resuspension and mobilization through bank interaction. The results informed source control and remedy design and monitoring efforts. Methodology and results from the South River have been published in peer-reviewed literature<ref name="ChangEtAl2018"/>.  
+
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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The U.S. Department of Defense’s Environmental Security Technology Certification Program (ESTCP) supported an OPTICS demonstration study at the Pearl Harbor Sediment Site, Hawaii, to determine whether stormwater from Oscar 1 Pier outfall is a contributing source of PCBs to Decision Unit (DU) N-2 (ESTCP Project ER21-5021). High spatial resolution results afforded by ship-based, mobile OPTICS monitoring suggested that PCBs were discharged from the outfall, remained in suspension, and dispersed elsewhere before settling (Figure 5). More details regarding this study were presented by Chang et al. in 2024<ref name="ChangEtAl2024"/>.
+
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==
 
==Summary==
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OPTICS provides:
+
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.
−
*High resolution surface water chemical contaminant characterization
+
<br clear="right"/>
−
*Cost-effective monitoring and assessment
 
−
*Versatile and modular monitoring with capability for real-time telemetry
 
−
*Data necessary for development and validation of conceptual site models
 
−
*A key line of evidence for designing and evaluating remedies.
 
−
 
 
−
Because OPTICS monitoring involves deployment of autonomous sampling instrumentation, a substantially greater volume of data can be collected using this technique compared to traditional sampling, and at a far lower cost. A large volume of data supports evaluation of chemical contaminant concentrations over a range of spatial and temporal scales, and the system can be customized for a variety of environmental applications. OPTICS helps quantify contaminant mass flux and the relative contribution of local transport and source areas to net contaminant transport. OPTICS delivers a strong line of evidence for evaluating contaminant sources, fate, and transport, and for supporting the design of a remedy tailored to address site-specific, risk-driving conditions. The improved understanding of site processes aids in the development of mitigation measures that minimize site risks.  
 
  
 
==References==
 
==References==
Line 66: Line 63:
  
 
==See Also==
 
==See Also==
 +
[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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