title: Implications of surfactant-induced flow for miscible-displacement estimation of air-water interfacial areas in unsaturated porous media.
abstract: Surfactant miscible-displacement experiments represent a conventional means of estimating air-water interfacial area (A(I)) in unsaturated porous media. However, changes in surface tension during the experiment can potentially induce unsaturated flow, thereby altering interfacial areas and violating several fundamental method assumptions, including that of steady-state flow. In this work, the magnitude of surfactant-induced flow was quantified by monitoring moisture content and perturbations to effluent flow rate during miscible-displacement experiments conducted using a range of surfactant concentrations. For systems initially at 83% moisture saturation (S(W)), decreases of 18-43% S(W) occurred following surfactant introduction, with the magnitude and rate of drainage inversely related to the surface tension of the surfactant solution. Drainage induced by 0.1 mM sodium dodecyl benzene sulfonate, commonly used for A(I) estimation, resulted in effluent flow rate increases of up to 27% above steady-state conditions and is estimated to more than double the interfacial area over the course of the experiment. Depending on the surfactant concentration and the moisture content used to describe the system, A(I) estimates varied more than 3-fold. The magnitude of surfactant-induced flow is considerably larger than previously recognized and casts doubt on the reliability of A(I) estimation by surfactant miscible-displacement.
authors.affiliation: Program for Environmental Studies and Department of Chemistry and Biochemistry, Middlebury College, 287 Bicentennial Way, Middlebury, Vermont 05753, USA. mcostanz@middlebury.edu
authors.forename: Molly S
authors.initials: MS
authors.lastname: Costanza-Robinson
authors.forename: Zheng
authors.initials: Z
authors.lastname: Zheng
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Henry
authors.forename: Benjamin D
authors.initials: BD
authors.lastname: Estabrook
authors.forename: Malcolm H
authors.initials: MH
authors.lastname: Littlefield
mesh_terms: D000388:Air; D001557:Benzenesulfonates / Q000737:chemistry; D004784:Environmental Monitoring / Q000379:methods*; D007700:Kinetics; D008956:Models, Chemical; D016062:Porosity; D013500:Surface Tension; D013501:Surface-Active Agents / Q000737:chemistry*; D014867:Water; D014874:Water Pollutants, Chemical / Q000737:chemistry*
chemical_list: D001557:Benzenesulfonates; D013501:Surface-Active Agents; D014874:Water Pollutants, Chemical; D014867:Water; C001114:dodecylbenzenesulfonic acid