View source for In Situ Groundwater Treatment with Activated Carbon

Emplacement of activated carbon (AC) into the subsurface is an emerging technology for ''in situ'' remediation. The technology has two components: activated carbon, which has high adsorption capacity for contaminants, and secondary chemical or biological amendments to stimulate ''in situ'' contaminant transformation. AC-based technology has been primarily applied at petroleum and chlorinated solvent contaminated sites where complex hydrogeology results in persistent plumes. 

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'''CONTRIBUTOR(S):''' [[Dr. Dimin Fan]]


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*[//www.enviro.wiki/images/e/e2/2018-USEPA._Remedial_Technology_Fact_Sheet.pdf  Remedial Technology Fact Sheet - Activated Carbon-Based Technology for In Situ Remediation]<ref name="USEPA2018RT">U.S. Environmental Protection Agency (USEPA), 2018. Remedial Technology Fact Sheet - Activated Carbon-Based Technology for In Situ Remediation. EPA 542-f-18-001. [//www.enviro.wiki/images/e/e2/2018-USEPA._Remedial_Technology_Fact_Sheet.pdf  Report.pdf]</ref>.
*[https://clu-in.org/techfocus/default.focus/sec/Activated_Carbon-Based_Technology_for_In_Situ_Remediation/cat/Overview/ CLU-IN Technology Focus Area: Activated Carbon-Based Technology for In Situ Remediation]

==Introduction==
AC-based technology involves ''in situ'' emplacements of AC-based amendments in the subsurface to form an adsorptive/reactive zone for contaminant remediation<ref>Fan, D., Gilbert, E.J. and Fox, T., 2017. Current state of in situ subsurface remediation by activated carbon-based amendments. Journal of Environmental Management, 204, pp.793-803. [https://doi.org/10.1016/j.jenvman.2017.02.014 doi: 10.1016/j.jenvman.2017.02.014]</ref><ref name="USEPA2018RT" />.  As contaminated groundwater flows through this zone, the contaminants are retarded due to adsorption on to activated carbon. Sorption increases the residence time of contaminants within the reactive zone and therefore also increases contact with the reactive amendments, which has the potential to promote contaminant degradation. 

==Fundamental Processes==

===Adsorption=== 
Common organic contaminants are sorbed by AC mainly through [https://en.wikipedia.org/wiki/Van_der_Waals_force van der Waals forces]. Adsorption is reversible under typical subsurface conditions, so contaminants may be released if water chemistry changes or competing solutes are present<ref>To, P.C., Mariñas, B.J., Snoeyink, V.L. and Ng, W.J., 2008. Effect of strongly competing background compounds on the kinetics of trace organic contaminant desorption from activated carbon. Environmental Science & Technology, 42(7), pp.2606-2611. [https://doi.org/10.1021/es702609r doi: 10.1021/es702609r]</ref>.  The large adsorption capacity of AC is due to its highly porous internal structure and is influenced by many factors, including solution chemistry and presence of co-contaminants or dissolved organic matter (DOM) that compete for sorption sites.  Chemical and biological processes can also alter the AC, potentially reducing adsorption capacity. Regeneration of AC with persulfate can increase the polar functional groups that contain oxygen on the surface, reducing adsorption capacity<ref>Huling, S.G., Ko, S., Park, S. and Kan, E., 2011. Persulfate oxidation of MTBE-and chloroform-spent granular activated carbon. Journal of Hazardous Materials, 192(3), pp.1484-1490. [https://doi.org/10.1016/j.jhazmat.2011.06.070 doi: 10.1016/j.jhazmat.2011.06.070]</ref><ref>Hutson, A., Ko, S. and Huling, S.G., 2012. Persulfate oxidation regeneration of granular activated carbon: reversible impacts on sorption behavior. Chemosphere, 89(10), pp.1218-1223. [https://doi.org/10.1016/j.chemosphere.2012.07.040 doi: 10.1016/j.chemosphere.2012.07.040]</ref>.  Organic compounds released by microorganisms can compete for sorption sites, similar to DOM<ref>Aktaş, Ö., Schmidt, K.R., Mungenast, S., Stoll, C. and Tiehm, A., 2012. Effect of chloroethene concentrations and granular activated carbon on reductive dechlorination rates and growth of Dehalococcoides spp. Bioresource Technology, 103(1), pp.286-292. [https://doi.org/10.1016/j.biortech.2011.09.119 doi: 10.1016/j.biortech.2011.09.119]</ref><ref>Zhao, X., Hickey, R.F. and Voice, T.C., 1999. Long-term evaluation of adsorption capacity in a biological activated carbon fluidized bed reactor system. Water Research, 33(13), pp.2983-2991. [https://doi.org/10.1016/S0043-1354(99)00014-7 doi: 10.1016/S0043-1354(99)00014-7]</ref>. These factors are more likely to impact ''in situ'' treatment performance than that of above-ground engineered reactors due to the lack of process controls. For example, pre-treatment to remove metals and periodic backwash are both commonly used in ''ex situ'' treatment to improve the performance of activated carbon reactors, but are not practical for ''in situ'' applications. 

===Effects of Activated Carbon on Degradation===
A variety of commercially available AC-based technologies have been developed in which AC is combined with [http://enviro.wiki/index.php?title=Zerovalent_Iron_(ZVI)_(Chemical_Reduction_-_ISCR) zero valent iron], [http://enviro.wiki/index.php?title=Chemical_Oxidation_(In_Situ_-_ISCO) chemical oxidants], or [http://enviro.wiki/index.php?title=Bioremediation_-_Anaerobic organic amendments] to stimulate contaminant degradation.  

AC has also been shown to increase the longevity of abiotic dechlorination mediated by ZVI when ZVI is impregnated within the AC pore matrix<ref>Choi, H., Al-Abed, S.R. and Agarwal, S., 2009. Effects of aging and oxidation of palladized iron embedded in activated carbon on the dechlorination of 2-chlorobiphenyl. Environmental Science & Technology, 43(11), pp.4137-4142. [https://doi.org/10.1021/es803535b doi: 10.1021/es803535b]</ref><ref>Tseng, H.H., Su, J.G. and Liang, C., 2011. Synthesis of granular activated carbon/zero valent iron composites for simultaneous adsorption/dechlorination of trichloroethylene. Journal of Hazardous Materials, 192(2), pp.500-506. [https://doi.org/10.1016/j.jhazmat.2011.05.047 doi: 10.1016/j.jhazmat.2011.05.047]</ref>. This has been attributed to AC protecting ZVI from other side reactions that can consume Fe(0), such as reduction of water. The enhanced longevity of abiotic dechlorination has also been observed in one pilot test in which Carbo-Iron® &reg; was injected into a contaminated aquifer<ref>Mackenzie, K., Bleyl, S., Kopinke, F.D., Doose, H. and Bruns, J., 2016. Carbo-Iron as improvement of the nanoiron technology: From laboratory design to the field test. Science of the Total Environment, 563, pp.641-648. [https://doi.org/10.1016/j.scitotenv.2015.07.107 doi: 10.1016/j.scitotenv.2015.07.107]</ref><ref>Vogel, M., Nijenhuis, I., Lloyd, J., Boothman, C., Pöritz, M. and Mackenzie, K., 2018. Combined chemical and microbiological degradation of tetrachloroethene during the application of Carbo-Iron at a contaminated field site. Science of The Total Environment, 628, pp.1027-1036. [https://doi.org/10.1016/j.scitotenv.2018.01.310 doi: 10.1016/j.scitotenv.2018.01.310]</ref>. 

AC addition has the potential to both enhance and inhibit biotransformation reactions.  In ''ex situ'' water treatment applications, the large surface area of AC can promote microbial attachment and biofilm formation, enhancing some biodegradation processes<ref>Simpson, D.R., 2008. Biofilm processes in biologically active carbon water purification. Water Research, 42(12), pp.2839-2848. [https://doi.org/10.1016/j.watres.2008.02.025 doi: 0.1016/j.watres.2008.02.025]</ref><ref>Bushnaf, K.M., Mangse, G., Meynet, P., Davenport, R.J., Cirpka, O.A. and Werner, D., 2017. Mechanisms of distinct activated carbon and biochar amendment effects on petroleum vapour biofiltration in soil. Environmental Science: Processes & Impacts, 19(10), pp.1260-1269. [https://doi.org/10.1039/c7em00309a doi: 10.1039/C7EM00309A]</ref>).  Recently, AC-supported biofilms were shown to enhance the extent of dechlorination of polychlorinated biphenyls (PCBs) in sediment<ref>Kjellerup, B.V., Naff, C., Edwards, S.J., Ghosh, U., Baker, J.E. and Sowers, K.R., 2014. Effects of activated carbon on reductive dechlorination of PCBs by organohalide respiring bacteria indigenous to sediments. Water Research, 52, pp.1-10. [https://doi.org/10.1016/j.watres.2013.12.030 doi: 10.1016/j.watres.2013.12.030]</ref>, and of RDX in granular activated carbon (Bio-GAC) reactors<ref>Millerick, K., Drew, S.R. and Finneran, K.T., 2013. Electron shuttle-mediated biotransformation of hexahydro-1, 3, 5-trinitro-1, 3, 5-triazine adsorbed to granular activated carbon. Environmental science & technology, 47(15), pp.8743-8750. [https://doi.org/10.1021/es401641s doi: 10.1021/es401641s]</ref>.  Adsorption to AC also has the potential to decrease contaminant availability for degradation because (''i'') micropores, the major sorption sites, are located deep in the AC pore matrix, which are physically separated from reactive amendments, and (''ii'') most degradation reactions require contaminants in the dissolved phase. If degradation processes cause aqueous phase concentration to decline, contaminants can desorb from the AC allowing further degradation.  

AC addition could potentially enhance some biotransformation processes by facilitating direct interspecies electron transfer (DIET)<ref>Lovley, D.R., 2017. Syntrophy goes electric: direct interspecies electron transfer. Annual Review of Microbiology, 71, pp.643-664. [https://doi.org/10.1146/annurev-micro-030117-020420 doi: 10.1146/annurev-micro-030117-020420]</ref>.  AC addition to anaerobic digesters has been shown to increase methane production.  Electrons produced during fermentation processes or hydrogen oxidation can be transferred through the AC to methanogens co-located on the activated carbon<ref>Liu, F., Rotaru, A.E., Shrestha, P.M., Malvankar, N.S., Nevin, K.P. and Lovley, D.R., 2012. Promoting direct interspecies electron transfer with activated carbon. Energy & Environmental Science, 5(10), pp.8982-8989. [https://doi.org/10.1039/c2ee22459c doi: 10.1039/c2ee22459c]</ref><ref>Yang, Y., Zhang, Y., Li, Z., Zhao, Z., Quan, X. and Zhao, Z., 2017. Adding granular activated carbon into anaerobic sludge digestion to promote methane production and sludge decomposition.  Journal of Cleaner Production, 149, pp.1101-1108. [https://doi.org/10.1016/j.jclepro.2017.02.156 doi:10.1016/j.jclepro.2017.02.156]</ref>).  However, the impact of AC addition on DIET in the subsurface has not been studied.

AC can be produced from a variety of different materials with different activation methods, pretreatments, and impregnations. These differences result in differing physical and chemical properties which can impact degradation processes. In recent laboratory studies, complete biological reductive dechlorination was inhibited in the presence of two different kinds of AC<ref>McGee, Kameryn and K.T. Finneran, In situ activated carbon for TCE remediation, ASM Microbe General Meeting, June 2018, to be presented in Atlanta, GA</ref>. These results are in contrast with the laboratory and field data reported for a commercial AC product, which have shown positive effects of AC on biological reductive dechlorination<ref>Valentine, M. Accelerate biodegradation of chlorinated contaminants facilitated using an in-situ liquid activated carbon: A pilot study and full-scale application in South Carolina. RemTEC 2017, Denver, CO. </ref>. The mechanisms that cause such a contrast are currently unknown, highlighting the need for further research. 

==State of Practice==
The first AC-based product for ''in situ'' groundwater remediation was developed in 2004. Since then, five more AC-based products have been developed (Table 1). Interests from practitioners and regulators have grown with increasing availability of commercial products. Together, these products have been applied at sites across North America and Europe. The largest proportion of applications have been at small retail gas station sites, focusing on treatment of petroleum constituents, primarily benzene, toluene, ethylbenzene and xylenes (BTEX).  However, the technology has been increasingly applied at large federal sites, such as Superfund sites, where chlorinated solvents are the major contaminants of concern<ref name="USEPA2018RT" />. 

{| class="wikitable" style="text-align: center; margin-left: auto; margin-right: auto;"
|+Table 1. Properties of seven AC-based products that have been used for ''in situ'' applications
|-
!Product
!Property
!Target Contaminants
!Degradation Pathway
|-
|BOS-100&reg;||Granular AC impregnated with ZVI||Chlorinated solvents||Abiotic reductive dechlorination
|-
|BOS-200&reg;||Powder AC mixed with nutrients, electron acceptors, and facultative bacteria||Petroleum hydrocarbons||Aerobic and anaerobic biodegradation
|-
|CAT-100&reg;||BOS-100&reg; plus reductive dechlorination bacterial strains||Chlorinated solvents||Abiotic and biotic reductive dechlorination
|-
|COGAC&reg;||Powder AC mixed with calcium peroxide and sodium persulfate||Chlorinated solvents or petroleum hydrocarbons||Chemical oxidation, aerobic and anaerobic biodegradation
|-
|PlumeStop&reg;||Colloidal AC suspension with a proprietary organic stabilizer, co-applied with hydrogen or oxygen release compounds, and/or corresponding bacterial strains||Chlorinated solvents or petroleum hydrocarbons||Biotic reductive dechlorination of chlorinated solvents or aerobic biodegradation of petroleum hydrocarbons
|-
|Carbo-Iron&reg;||Colloidal AC impregnated with ZVI||Chlorinated solvents||Abiotic reductive dechlorination
|-
|EHC-Plus&reg;||35% (wt) microscale ZVI, 50% controlled-release organic carbon, 15% powder AC||Chlorinated solvents||Abiotic and biotic reductive dechlorination
|}

==Treatment Scenario==
AC-based technology has been primarily applied for management of persistent plumes resulting from the slow release of contaminants from low permeability zones (see [http://enviro.wiki/index.php?title=Dispersion_and_Diffusion Dispersion and Diffusion]).  The combination of ''in situ'' adsorption and degradation is thought to be more cost-effective than pump & treat (P&T) and sustain longer treatment effectiveness than degradation alone. Several field applications have demonstrated long-term effectiveness of AC-based technology<ref>Guilfoil, D., 2017. Karst bedrock remediation of PCE in Kentucky. 33rd Annual International Conference on Soils, Sediments, Water, and Energy. Amherst, MA</ref>. However, questions remain about whether adsorption or degradation is the primary process responsible for contaminant removal. 

This technology has also been used to limit contaminant migration from groundwater to surface water, where high groundwater velocity limited the effectiveness of soluble amendments<ref>Krouse, C.; Fitzgerald, S.; Noland, S.; Thacker, N., 2016. Angled injection to mitigate PCE intrusion into a stream at a Federal superfund site in the Piedmont Region of North Carolina, 10th International Conference on Remediation of Chlorinated and Recalcitrant Compounds. Palm Springs, CA.</ref>.  

==Implementation==
Implementation of ''in situ'' AC-based technologies follows similar design principles and engineering approaches as any other injection-based remediation technology. Subsurface hydrogeology and contaminant distribution, both vertically and horizontally, must be well understood and delineated.  Colloidal AC products can be injected under low pressure and transported through high permeability zones to reduce mass flux.  GAC and PAC-based products must be injected under pressure and are not expected to transport substantial distances.  The design loading rate of GAC and PAC-based products is typically determined by total mass of a contaminant in both high and low permeability zones.  The design loading rate of colloidal AC-based products is based on the dissolved contaminant mass flux. 

Performance monitoring for ''in situ'' AC-based remedial technology requires multiple lines of evidence to confirm that contaminants are removed not only by adsorption but also by degradation. Reduction in concentration of parent compounds alone cannot differentiate degradation from adsorption.  If [http://enviro.wiki/index.php?title=Biodegradation_-_Reductive_Processes reductive dechlorination] is thought to be an important degradation process, treatment performance should be evaluated by monitoring for complete dechlorination products (e.g., ethene/ethane) and molecular indicators (e.g., ''Dehalococcoides'' population or presence of vinyl chloride reductase (''vcrA'')). For [http://enviro.wiki/index.php?title=Biodegradation_-_Hydrocarbons petroleum hydrocarbons], consumption of electron acceptors (e.g., nitrate or sulfate) or production of volatile fatty acids (VFAs) may serve as general indicators for biological degradation. [http://enviro.wiki/index.php?title=Molecular_Biological_Tools_-_MBTs Molecular diagnostic tools] may provide more definitive evidence by targeting specific functional genes necessary for biodegradation.  

==References==

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==See Also==