Abstract
The purpose of this study is to investigate the elution behavior of pool-dominated dense nonaqueous phase liquid (DNAPL) source zone mass during enhanced solubilization remediation. Flow-cell experiments were first conducted to investigate the performance of different solubilization agents on the DNAPL source zone mass removal in porous media. PCE was used as the model organic liquid, while sodium dodecyl sulfate and Tween 80 surfactants, methyl cyclodextrin (MCD) were selected as enhanced-flushing agents. The porous media considered were silica sand and natural calcareous soil. To gain further insight into the dynamics of source zone depletion, the flushing experiments were modeled using two approaches: a multiphase flow model and a simplified empirically based concentration mass discharge (CMD) model. Results of the flushing experiments indicated that the performance of solubilization agents on PCE source zone depletion was in the following order: Tween 80 > SDS > MCD > > Water. Both models reveal the non-ideal behavior observed during the flooding experiments. For all cases considered, the later stage of mass removal appears to be controlled by the portion poorly accessible mass associated with higher-saturation zones. The advantages and limitations of the two modeling approaches are discussed. It is shown that the two modeling approaches are complementary to each other. Whereas the multiphase model can reveal important aspects of the governing pore-scale processes, the latter approach can provide valuable source term depletion metrics, circumventing the need for detailed definition of DNAPL and porous media parameters.
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The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.
References
Akgoze Aydin, G., Agaoglu, B., Kocasoy, G., & Copty, N. K. (2011). Effect of temperature on cosolvent flooding for the enhanced solubilization and mobilization of NAPLs in porous media. Journal of Hazardous Materials, 186, 636–644. https://doi.org/10.1016/j.jhazmat.2010.11.046
Agaoglu, B., Copty, N. K., Scheytt, T., & Hinkelmann, R. (2015). Interphase mass transfer between fluids in subsurface formations: A review. Advances in Water Resources, 79, 162–194. https://doi.org/10.1016/j.advwatres.2015.02.009
Akyol, N. H., Yolcubal, I., & Imer, D. Y. (2011). Sorption and transport of trichloroethylene in caliche soil. Chemosphere, 82, 809–816. https://doi.org/10.1016/j.chemosphere.2010.11.029
Akyol, N. H., & Yolcubal, I. (2013). Oxidation of nonaqueous phase trichloroethylene with permanganate in epikarst. Water, Air, & Soil Pollution, 224, 1573. https://doi.org/10.1007/s11270-013-1573-6
Akyol, N. H., Lee, A. R., & Brusseau, M. L. (2013). Impact of enhanced-flushing reagents and organic liquid distribution on mass removal and mass discharge. Water, Air, & Soil Pollution, 224, 1731. https://doi.org/10.1007/s11270-013-1731-x
Akyol, N. H., Ozbay, I., & Ozbay, B. (2015). Effect of organic carbon fraction on long-term atrazine elution tailing for two heterogeneous porous media: Experimental and modeling approach. Water, Air, & Soil Pollution, 226, 368. https://doi.org/10.1007/s11270-015-2639-4
Akyol, N. H. (2018). Surfactant-enhanced permanganate oxidation on mass-flux reduction and mass removal (MFR-MR) relationships for pool-dominated TCE source zones in heterogeneous porous media. Water, Air, & Soil Pollution, 229, 285. https://doi.org/10.1007/s11270-018-3946-3
Akyol, N. H., & Turkkan, S. (2018). Effect of cyclodextrin-enhanced dissolution on mass removal and mass-flux reduction relationships for non-uniformly organic liquid distribution in heterogeneous porous media. Water, Air, & Soil Pollution, 229, 30. https://doi.org/10.1007/s11270-017-3673-1
Aydin-Sarikurt, D., Dokou, Z., Copty, N. K., & Karatzas, G. P. (2016). Experimental investigation and numerical modeling of enhanced DNAPL solubilization in saturated porous media. Water, Air, & Soil Pollution, 227, 441. https://doi.org/10.1007/s11270-016-3136-0
Badr, T., Hanna, K., & de Brauer, C. (2004). Enhanced solubilization and removal of naphthalene and phenanthrene by cyclodextrins from two contaminated soils. Journal of Hazardous Materials, 112, 215–223. https://doi.org/10.1016/j.jhazmat.2004.04.017
Boving, T. B., & Brusseau, M. L. (2000). Solubilization and removal of residual Trichloroethene from porous media: Comparison of several solubilization agents. Journal of Contaminant Hydrology, 42, 51–67. https://doi.org/10.1016/S0169-7722(99)00077-7
Brooks, R. H., & Corey, A. T. (1966). Properties of porous media affecting fluid flow. Jornal of the Irrigation and Drainage Division, 92, 61–90. https://doi.org/10.1061/JRCEA4.0000425
Brusseau, M. L., Zhang, Z., Nelson, N. T., Cain, R. B., Tick, G. R., & Oostrom, M. (2002). Dissolution of nonuniformly distributed immiscible liquid: Intermediate-scale experiments and mathematical modeling. Environmental Science & Technology, 36, 1033–1041. https://doi.org/10.1021/es010609f
Brusseau, M. L., Nelson, N. T., Zhang, Z., Blue, J. E., Rohrer, J., & Allen, T. (2007). Source-zone characterization of a chlorinated solvent contaminated superfund site in Tucson AZ. Journal of Contaminant Hydrology, 90, 21–40. https://doi.org/10.1016/j.jconhyd.2006.09.004
Brusseau, M. L., DiFilippo, E. L., Marble, J. C., & Oostrom, M. (2008). Mass-removal and mass-flux-reduction behavior for idealized source zones with hydraulically poorly-accessible organic liquid. Chemosphere, 71, 1511–1521. https://doi.org/10.1016/j.chemosphere.2007.11.064
Brusseau, M. L., Matthieu, D. E., Carroll, K. C., Mainhagu, J., Morrison, C., McMillan, A., Russo, A., & Plaschke, M. (2013). Characterizing long-term contaminant mass discharge and the relationship between reductions in discharge and reductions in mass for DNAPL source areas. Journal of Contaminant Hydrology, 149, 1–12. https://doi.org/10.1016/j.jconhyd.2013.02.011
Burden, R & Faires, J.D. (1997). Sixth Edition, Numerical Analysis, Brooks/Coles Publishing
Carroll, K. C., & Brusseau, M. L. (2009). Dissolution, cyclodextrin-enhanced solubilization, and mass removal of an ideal multicomponent organic liquid. Journal of Contaminant Hydrology, 106, 62–72. https://doi.org/10.1016/j.jconhyd.2009.01.002
Cheng, Y., & Zhu, J. (2021). Significance of mass–concentration relation on the contaminant source depletion in the nonaqueous phase liquid (NAPL) contaminated zone. Transport in Porous Media, 137, 399–416. https://doi.org/10.1007/s11242-021-01567-5
Delshad, M., Pope, G. A., & Sepehrnoori, K. (1996). A compositional simulator for modeling surfactant enhanced aquifer remediation, 1 formulation. Journal of Contaminant Hydrology, 23, 303–327. https://doi.org/10.1016/0169-7722(95)00106-9
DiFilippo, E. L., & Brusseau, M. L. (2008). Relationship between mass flux reduction and source-zone mass removal: Analysis of field data. Journal of Contaminant Hydrology, 98, 22–35. https://doi.org/10.1016/j.jconhyd.2008.02.004
DiFilippo, E. L., Carroll, K. C., & Brusseau, M. L. (2010). Impact of organic-liquid distribution and flow-field heterogeneity on reductions in mass flux. Journal of Contaminant Hydrology, 115, 14–25. https://doi.org/10.1016/j.jconhyd.2010.03.002
DiGiulio, D. C., Ravi, V., & Brusseau, M. L. (1999). Evaluation of mass flux to and from ground water using a vertical flux model (VFLUX): Application to the soil vacuum extraction closure problem. Groundwater Monitoring & Remediation, 19, 96–104. https://doi.org/10.1111/j.1745-6592.1999.tb00210.x
Freeze, R. A., & McWhorter, D. B. (1997). A framework for assessing risk reduction due to DNAPL mass removal from low-permeability soils. Groundwater, 35, 111–123. https://doi.org/10.1111/j.1745-6584.1997.tb00066.x
Gelhar, L. W. (1993). Stochastic subsurface hydrology. Prentice-Hall.
Grimberg, S. J., Nagel, J., & Aitken, M. D. (1995). Kinetics of phenanthrene dissolution into water in the presence of nonionic surfactants. Environmental Science & Technology, 29, 1480–1487. https://doi.org/10.1021/es00006a008
Hand, D. B. (1930). Dineric distribution. The Journal of Physical Chemistry, 34, 1961–2000. https://doi.org/10.1021/j150315a009
Harvell, J.R. (2012). Solubilization of multi-component immiscible liquids in homogeneous systems: A comparison of different flushing agents using a 2-D flow cell. M.S. Thesis, University of Alabama, U.S.A
Horvath, A. L., Getzen, F. W., & Maczynska, Z. (1999). IUPAC-NIST solubility data series 67. Halogenated ethanes and ethenes with water. Journal of Physical and Chemical Reference Data, 28, 395–627. https://doi.org/10.1063/1.556039
Huh, C. (1979). Interfacial-tensions and solubilizing ability of a microemulsion phase that coexists with oil and brine. Journal of Colloid and Interface Science, 71, 408–426. https://doi.org/10.1016/0021-9797(79)90249-2
Johnson, J. C., Sun, S., & Jaffe, P. R. (1999). Surfactant enhanced perchloroethylene dissolution in porous media: The effect on mass transfer rate coefficients. Environmental Science & Technology, 33, 1286–1292. https://doi.org/10.1021/es980908d
Kennedy, C. A., & Lennox, W. C. (1997). A pore-scale investigation of mass transport from dissolving DNAPL droplets. Journal of Contaminant Hydrology, 24, 221–246. https://doi.org/10.1016/S0169-7722(96)00011-3
Kilavuz, S., & Akyol, N. (2018). In-situ remediation of TCE source zones by chemical flushing: Performance of Tween 80 and SDS. DEU-Faculty of Engineering Journal of Science and Engineering, 20, 197–208. https://doi.org/10.21205/deufmd.2018205817
Li, B., & Fu, J. (1992). Interfacial tensions of two-liquid-phase ternary systems. Journal of Chemical and Engineering Data, 37, 172–174. https://doi.org/10.1021/je00006a009
Liang, H., & Falta, R. W. (2008). Modeling field-scale cosolvent flooding for DNAPL source zone remediation. Journal of Contaminant Hydrology, 96, 1–16. https://doi.org/10.1016/j.jconhyd.2007.09.005
Mahal, M. K., Murao, A., Johnson, G. R., Russo, A., & Brusseau, M. L. (2010). Non-ideal behavior during complete dissolution of organic immiscible liquid: 2. Ideal porous media. Water, Air & Soil Pollution, 213, 191–197. https://doi.org/10.1007/s11270-010-0377-1
Mayer, A. S., Zhong, L., & Pope, G. A. (1999). Measurement of mass-transfer rates for surfactant-enhanced solubilization of nonaqueous phase liquids. Environmental Science & Technology, 33(17), 2965–2972.
McCray, J. E., & Brusseau, M. L. (1999). Cyclodextrin-enhanced in situ flushing of multiple component immiscible organic-liquid contamination at the field scale: Analysis of dissolution behavior. Environmental Science & Technology, 33, 89–95. https://doi.org/10.1021/es980117b
McCray, J. E., Boving, T. B., & Brusseau, M. L. (2000). Cyclodextrin-enhanced solubilization of organic contaminants with implications for aquifer remediation. Ground Water Monitoring and Remediation, 20, 94–103. https://doi.org/10.1111/j.1745-6592.2000.tb00256.x
Mohammed, M., Ozbay, I., Akyol, G., Akyol, N. H., Sahin, Y., Ozbay, B., Turkkan, S., & Karatas, T. (2019). Optimizing process parameters on the remediation efforts for the mass removal of DNAPL entrapped in a porous media. Water, Air & Soil Pollution, 230, 161. https://doi.org/10.1007/s11270-019-4191-0
Nambi, I. M., & Powers, S. E. (2000). NAPL dissolution in heterogeneous systems: An experimental investigation in a simple heterogeneous system. Journal of Contaminant Hydrology, 44, 161–184. https://doi.org/10.1016/S0169-7722(00)00095-4
Newell, C.J., Conner, J.A., & Rowen, D.L. (2003). Groundwater remediation strategies tool. Publ. No. 4730. Washington, D.C: American Petroleum Institute
Pankow, J. F., & Cherry, J. A. (1996). Dense chlorinated solvents and other DNAPLS in groundwater: History, Behavior, and Remediation. Waterloo Press.
Powers, S. E., Abriola, L. M., & Weber, W. J., Jr. (1994). An experimental investigation of nonaqueous phase liquid dissolution in saturated subsurface systems: Transient mass transfer rates. Water Resources Research, 30, 321–332. https://doi.org/10.1029/93WR02923
Rao, P.C., Jawitz, J.W., Enfield, C.G., Falta, R.W., Annable, M.D., & Wood, A.L. (2001). Technology integration for contaminated site remediation: Clean-up goals and performance criteria. Presented at Groundwater Quality 2001, Sheffield, England, 6/18–21/2001
Rosenbloom, J., Mock, P., Lawson, P., Brown, J., & Turin, H. J. (1993). Application of VLEACH to vadose zone transport of VOCs at an Arizona superfund site. Groundwater Monitoring & Remediation, 13, 159–169. https://doi.org/10.1111/j.1745-6592.1993.tb00085.x
Russo, A., Mahal, M. K., & Brusseau, M. L. (2009). Nonideal behavior during complete dissolution of organic immiscible liquid: 1. Natural porous media. Journal of Hazardous Materials, 172, 208–213. https://doi.org/10.1016/j.jhazmat.2009.06.160
Schwille, F. (1988). Dense chlorinated solvents in porous and fractured media (translated by J.F. Pankow). Lewis Publications, Chelsea, MI, pp. 144
Soga, K., Page, J. W. E., & Illangasekare, T. H. (2004). A review of NAPL source zone remediation efficiency and the mass flux approach. Journal of Hazardous Materials, 110, 13–27. https://doi.org/10.1016/j.jhazmat.2004.02.034
Stroo, H. F., Unger, M., Ward, C. H., Kavanaugh, M. C., Vogel, C., Leeson, A., Marqusee, J. A., & Smith, B. P. (2003). Remediating chlorinated solvent source zones. Environmental Science & Technology, 37, 224A-230A. https://doi.org/10.1021/es032488k
Tick, G. R., Lourenso, F., Wood, A. L., & Brusseau, M. L. (2003). Pilot-scale demonstration of cyclodextrin as a solubility-enhancement agent for the remediation of a tetrachloroethene-contaminated aquifer. Environmental Science & Technology, 37, 5829–5834. https://doi.org/10.1021/es030417f
Tick, G., & Rincon, E. (2009). Effect of enhanced solubilization agents on dissolution and mass flux from uniformly distributed immiscible liquid trichloroethylene (TCE) in homogeneous porous media. Water, Air & Soil Pollution, 204, 315–332. https://doi.org/10.1007/s11270-009-0047-3
Tick, G. R., Harvell, J. R., & Murgulet, D. (2015). Intermediate scale investigation of enhanced-solubilization agents on the dissolution and removal of a multicomponent dense nonaqueous phase liquid (DNAPL) source. Water, Air & Soil Pollution, 226, 371. https://doi.org/10.1007/s11270-015-2636-7
Volpe, A., Del Moro, G., Rossetti, S., Tandoi, V., & Lopez, A. (2007). Remediation of PCE-contaminated groundwater from an industrial site in southern Italy: A laboratory-scale study. Process Biochemistry, 42, 1498–1505. https://doi.org/10.1016/j.procbio.2007.07.017
Wang, X., & Brusseau, M. L. (1993). Solubilization of some low-polarity organic compounds by hydroxypropyl-B-cyclodextrin. Environmental Science & Technology, 27, 2821–2825. https://doi.org/10.1021/es00049a023
Yaksi, K., Demiray, Z., & Copty, N. K. (2021). Impact of cosolvents on the interphase mass transfer of NAPLs in porous media. Water Resources Research, 57, e2020WR029326. https://doi.org/10.1029/2020WR029326
Yalkowsky, S., He, Y., & Jain, P. (2016). Handbook of aqueous solubility data (2nd ed.). CRC Press. https://doi.org/10.1201/EBK1439802458
Yang, J. S., Baek, K., Kwon, T. S., & Yang, J. W. (2006). Competitive immobilization of multiple component chlorinated solvents by cyclodextrin derivatives. Journal of Hazardous Materials, 137, 1866–1869. https://doi.org/10.1016/j.jhazmat.2006.04.020
Valletti, N., Budroni, M. A., Lagzi, I., Marchettini, N., Sanchez-Dominguez, M., and Rossi, F. (2021). Interfacial mass transfer in trichloroethylene/surfactants/water systems: Implications for remediation strategies. Reactions, 2(3), 312–322. [online] https://doi.org/10.3390/reactions2030020.
Zheng, F., Gao, B., Sun, Y., Shi, X., Xu, H., Wu, J., & Gao, Y. (2016). Removal of tetrachloroethylene from homogeneous and heterogeneous porous media: Combined effects of surfactant solubilization and oxidant degradation. Chemical Engineering Journal, 283, 595–603. https://doi.org/10.1016/j.cej.2015.08.004
Zhong, L., Mayer, A. S., & Pope, G. A. (2003). The effects of surfactant formulation on nonequilibrium NAPL solubilization. Journal of Contaminant Hydrology, 60, 55–75. https://doi.org/10.1016/S0169-7722(02)00063-3
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This research was supported by TUBITAK (Project No. 117Y140).
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Demiray, Z., Akyol, N.H. & Copty, N.K. Experimental Assessment and Modeling of Enhanced Solubilization of Pool-dominated Tetrachloroethene Source Zone in Heterogeneous Porous Media. Water Air Soil Pollut 232, 516 (2021). https://doi.org/10.1007/s11270-021-05454-z
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DOI: https://doi.org/10.1007/s11270-021-05454-z