title: Surfactant-induced flow compromises determination of air-water interfacial areas by surfactant miscible-displacement.
abstract: Surfactant miscible-displacement (SMD) column experiments are used to measure air-water interfacial area (AI) in unsaturated porous media, a property that influences solute transport and phase-partitioning. The conventional SMD experiment results in surface tension gradients that can cause water redistribution and/or net drainage of water from the system ("surfactant-induced flow"), violating theoretical foundations of the method. Nevertheless, the SMD technique is still used, and some suggest that experimental observations of surfactant-induced flow represent an artifact of improper control of boundary conditions. In this work, we used numerical modeling, for which boundary conditions can be perfectly controlled, to evaluate this suggestion. We also examined the magnitude of surfactant-induced flow and its impact on AImeasurement during multiple SMD flow scenarios. Simulations of the conventional SMD experiment showed substantial surfactant-induced flow and consequent drainage of water from the column (e.g., from 75% to 55% SW) and increases in actual AIof up to 43%. Neither horizontal column orientation nor alternative boundary conditions resolved surfactant-induced flow issues. Even for simulated flow scenarios that avoided surfactant-induced drainage of the column, substantial surfactant-induced internal water redistribution occurred and was sufficient to alter surfactant transport, resulting in up to 23% overestimation of AI. Depending on the specific simulated flow scenario and data analysis assumptions used, estimated AIvaried by nearly 40% and deviated up to 36% from the system's initial AI. We recommend methods for AIdetermination that avoid generation of surface-tension gradients and urge caution when relying on absolute AIvalues measured via SMD.
authors.affiliation: Middlebury College, Program for Environmental Studies, Department of Chemistry & Biochemistry, 276 Bicentennial Way, Middlebury, VT 05753, USA. Electronic address: smcostanz@middlebury.edu.
authors.forename: Molly S
authors.initials: MS
authors.lastname: Costanza-Robinson
authors.affiliation: University of North Carolina-Wilmington, Department of Geography and Geology, 601 South College Road, Wilmington, NC 28403, USA. Electronic address: ericjhenry5@gmail.com.
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Henry
mesh_terms: D000388:Air; D004784:Environmental Monitoring / Q000379:methods*; D016062:Porosity; D012996:Solutions; D013500:Surface Tension; D013501:Surface-Active Agents / Q000737:chemistry*; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry*
chemical_list: D012996:Solutions; D013501:Surface-Active Agents; D014874:Water Pollutants, Chemical; D014867:Water
keywords: Air-water interfacial area; Modeling; Surfactant-induced flow; Tracer tests; Unsaturated flow