Water, Air, & Soil Pollution

, 227:379 | Cite as

A Methodological Approach to Assess the Dissolution of Residual LNAPL in Saturated Porous Media and Its Effect on Groundwater Quality: Preliminary Experimental Results

  • Eleonora Frollini
  • Daniela Piscitelli
  • Iason Verginelli
  • Renato Baciocchi
  • Marco PetittaEmail author


In this paper, we present a simple methodological approach to assess the dissolution behaviour of residual light nonaqueous phase liquid (LNAPL) sources entrapped in saturated porous media and to estimate the actual risk to human health by water ingestion related to their presence in the subsurface. The approach consists of collecting experimental data on the release kinetics through lab-scale column tests and including these data in a modified version of the analytical model used to describe the groundwater ingestion pathway in risk analysis. The approach was applied to different test scenarios using toluene as a model compound and three types of porous media, i.e. glass beads and two sandy soils with slightly different textures. The experimental results showed that the concentration of toluene in the eluted water was far from the solubility value after a limited number of pore volumes. Furthermore, different behaviour was observed for the three types of porous media. In particular, higher residual saturation and a slower dissolution rate were observed for the soil characterized by the finest texture. This behaviour suggests that the release rate is inversely proportional to the total residual saturation due to the reduction in the porosity available for water flow and the permeability of the porous media. Using these data in a modified risk-based model showed that a remarkable reduction of the hazard index related to the water ingestion pathway can be achieved for a relatively high groundwater velocity and a small contamination source.


LNAPL Dissolution experiments Porous media Column test Risk assessment 


  1. Adepelumi, A. A., Solanke, A. A., Sanusi, O. B., & Shallangwa, A. M. (2006). Model tank electrical resistivity characterization of LNAPL migration in a clayey-sand formation. Environmental Geology, 50(8), 1221–1233.CrossRefGoogle Scholar
  2. APAT (2008). Criteri metodologici per l’applicazione dell’analisi assoluta di rischio ai siti contaminati, available at Scholar
  3. ASTM. (2000). Standard guide for risk-based corrective action (pp. E2081–00). West Conshohocken: ASTM.Google Scholar
  4. Baciocchi, R., Berardi, S., & Verginelli, I. (2010). Human health risk assessment: models for predicting the effective exposure duration of on-site receptors exposed to contaminated groundwater. Journal of Hazardous Materials, 181, 226–233.CrossRefGoogle Scholar
  5. Bao, W. M. J., Vogler, E. T., & Chrysikopoulos, C. V. (2003). Nonaqueous liquid pool dissolution in three-dimensional heterogeneous subsurface formations. Environmental Geology, 43, 968–977.Google Scholar
  6. Boving, T. B., & Brusseau, M. L. (2000). Solubilization and removal of residual trichloroethane from porous media: comparison of several solubilization agents. Journal of Contaminant Hydrology, 42, 51–67.CrossRefGoogle Scholar
  7. Boving, T. B., Wang, X., & Brusseau, M. L. (1999). Cyclodextrin-enhanced solubilization and removal of residual-phase chlorinated solvents from porous media. Environmental Science and Technology, 33(5), 764–770.CrossRefGoogle Scholar
  8. Carlon, C. (2007). Derivation methods of soil screening values in Europe. A review and evaluation of national procedures towards harmonization. European Commission, Joint Research Centre, Ispra, EUR 22805-EN, 306 pp.Google Scholar
  9. 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.CrossRefGoogle Scholar
  10. Chapman, S. W., Parker, B. L., Sale, T. C., & Doner, L. A. (2012). Testing high resolution numerical models for analysis of contaminant storage and release from low permeability zones. Journal of Contaminant Hydrology, 136–137, 106–116.CrossRefGoogle Scholar
  11. Cherry, J. A., Parker, B. L., Bradbury, K. R., Eaton, T. T., Gotkowitz, M. B., Hart, D. J., & Borchardt, M. M. (2006). Contaminant transport through aquitards: a “state of the science” review. In American Water Works Association Awwa (Ed.), Research Foundation, and International Water Well Association. Denver: IWA.Google Scholar
  12. Devlin, J. F. (2015). HydrogeoSieveXL: an Excel-based tool to estimate hydraulic conductivity from grain-size analysis. Hydrogeology Journal, 23, 837–844.CrossRefGoogle Scholar
  13. EPA (2015). US Environmental Protection Agency, Toxicity and chemical/physical properties for regional screening level (RSL) of chemical contaminants at superfund sites, available at
  14. Feenstra, S. (2005). Soil sampling in NAPL source zones: challenges to representativeness. Environmental Forensics, 6, 57–63.CrossRefGoogle Scholar
  15. ISS-INAIL (2015). Banca dati ISS-INAIL per Analisi di Rischio Sanitario Ambientale, available at
  16. Jones, E. H., & Smith, C. C. (2005). Non-equilibrium partitioning tracer transport in porous media: 2-D physical modeling and imaging using a partitioning fluorescent die. Water Research, 39, 5099–5111.CrossRefGoogle Scholar
  17. Kamaruddin SA, Sulaiman WNA, Zakaria MP, Othman R, Rahman NA (2011). Laboratory simulation of LNAPL spills and remediation in unsaturated porous media using the image analysis technique: a review. National Postgraduate Conference (NPC), 2011, pp. 1–7, 19–20 Sept 2011. doi  10.1109/NatPC.201.6136348
  18. Karapanagioti, H. K., Gaganis, P., & Burganos, V. N. (2003). Modeling attenuation of volatile organic mixtures in the unsaturated zone: codes and usage. Environmental Modelling and Software, 18, 329–337.CrossRefGoogle Scholar
  19. Kechavarzi, C., Soga, K., & Illangasekare, T. H. (2005). Two-dimensional laboratory simulation of LNAPL infiltration and redistribution in the vadose zone. Journal of Contaminant Hydrology, 76, 211–233.CrossRefGoogle Scholar
  20. Lambe TW, Whitman RV (1969). Soil mechanics. New York: Wiley.Google Scholar
  21. Liu, C., & Ball, W. P. (2002). Back diffusion of chlorinated solvent contaminants from a natural aquitard to a remediated aquifer under well-controlled field conditions: predictions and measurements. Ground Water, 40(2), 175–184.CrossRefGoogle Scholar
  22. Mercer, J. W., & Cohen, R. M. (1990). A review of immiscible fluids in the subsurface: properties, models, characterization and remediation. Journal of Contaminant Hydrology, 6, 107–163.CrossRefGoogle Scholar
  23. Mobile, M., Widdowson, M., Stewart, L., Nyman, J., Deeb, R., Kavanaugh, M., Mercer, J., & Gallagher, D. (2016). In-situ determination of field-scale NAPL mass transfer coefficients: performance, simulation and analysis. Journal of Contaminant Hydrology, 187, 31–46.CrossRefGoogle Scholar
  24. 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.CrossRefGoogle Scholar
  25. Nambi, I. M., & Powers, S. E. (2003). Mass transfer correlations for nonaqueous phase liquid dissolution from regions with high initial saturations. Water Resources Research, 39(2), 1030. doi: 10.1029/2001WR000667.CrossRefGoogle Scholar
  26. Page, J. W. E., Soga, K., & Illangasekare, T. (2007). The significance of heterogeneity on mass flux from DNAPL source zones: an experimental investigation. Journal of Contaminant Hydrology, 94, 215–234.CrossRefGoogle Scholar
  27. Parker, B. L., Chapman, S. W., & Gilbeault, M. A. (2008). Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation. Journal of Contaminant Hydrology, 102, 86–104.CrossRefGoogle Scholar
  28. Piscitelli, D., Zingaretti, D., Verginelli, I., Gavasci, R., & Baciocchi, R. (2015). The fate of MtBE during Fenton-like treatments through laboratory scale column tests. Journal of Contaminant Hydrology, 183, 99–108.CrossRefGoogle Scholar
  29. Powers, S. E., Abriola, L. M., & Weber, W. J. (1992). An experimental investigation of nonaqueous phase liquid dissolution in saturated subsurface systems: steady state mass transfer rates. Water Resources Research, 28(10), 2691–2705.CrossRefGoogle Scholar
  30. Puigserver, D., Carmona, J. M., Cortés, A., Viladevall, M., Nieto, J. M., Grifoll, M., Vila, J., & Parker, B. L. (2013). Subsoil heterogeneities controlling porewater contaminant mass and microbial diversity at a site with a complex pollution history. Journal of Contaminant Hydrology, 144, 1–19.CrossRefGoogle Scholar
  31. Saba, T., & Illangasekare, T. H. (2000). Effect of groundwater flow dimensionality on mass transfer from entrapped nonaqueous phase liquid contaminants. Water Resources Research, 36(4), 971–979.CrossRefGoogle Scholar
  32. Seagren, E. A., Rittmann, B. E., & Valocchi, A. J. (1999). An experimental investigation of NAPL pool dissolution enhancement by flushing. Journal of Contaminant Hydrology, 37, 111–137.CrossRefGoogle Scholar
  33. Shin, H.-S., & Kim, T.-S. (2009). Analysis of tert-butanol, methyl tert-butyl ether, benzene, toluene ethylbenzene and xylene in ground water by headspace gas chromatography-mass spectrometry. Bulletin of the Korean Chemical Society, 30(12), 3049–3052.CrossRefGoogle Scholar
  34. Spitz K, Moreno J. (1996). A practical guide to groundwater and solute transport modeling. New York: John Wiley & Sons, Inc.Google Scholar
  35. Sulaymon, A. H., & Gzar, H. A. (2011). Experimental investigation and numerical modeling of light nonaqueous phase liquid dissolution and transport in a saturated zone of the soil. Journal of Hazardous Materials, 186, 1601–1614.CrossRefGoogle Scholar
  36. Thomson, N. R., Graham, D. N., & Farquhar, G. J. (1992). One-dimensional immiscible displacement experiments. Journal of Contaminant Hydrology, 10, 197–223.CrossRefGoogle Scholar
  37. USEPA (1990). Laboratory investigation of residual liquid organics from spills, leaks, and the disposal of hazardous wastes in groundwater. EPA/600/6-90/004Google Scholar
  38. Verginelli, I., & Baciocchi, R. (2013). Role of natural attenuation in modeling the leaching of contaminants in the risk analysis framework. Journal of Environmental Management, 114, 395–403.CrossRefGoogle Scholar
  39. Verginelli, I., & Baciocchi, R. (2014). Vapor intrusion screening model for the evaluation of risk-based vertical exclusion distances at petroleum contaminated sites. Environmental Science and Technology, 48(22), 13263–13272.CrossRefGoogle Scholar
  40. Verginelli, I., Capobianco, O., & Baciocchi, R. (2016). Role of the source to building lateral separation distance in petroleum vapor intrusion. Journal of Contaminant Hydrology, 189, 58–67.CrossRefGoogle Scholar
  41. Zhang, W., Thompson, K. E., Reed, A. H., & Beenken, L. (2006). Relationship between packing structure and porosity in fixed beds of equilateral cylindrical particles. Chemical Engineering Science, 61, 8060–8074.CrossRefGoogle Scholar
  42. Zhang, J., Zheng, X., Chen, L., & Sun, Y. (2014). Effect of residual oil saturation on hydrodynamic properties of porous media. Journal of Hydrology, 515, 281–291.CrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2016

Authors and Affiliations

  1. 1.Earth Sciences DepartmentSapienza University of RomeRomeItaly
  2. 2.Laboratory of Environmental Engineering, Department of Civil Engineering and Computer Science EngineeringUniversity of Rome “Tor Vergata”RomeItaly

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