Aqueous solutions of micro-nano bubbles (MNBs) containing ozone gas were injected through a NAPL-contaminated glass bead column. The glass column (15 cm x 2.5 cm) was packed with glass beads: the first 12 cm was packed with coarse glass beads while much finer glass beads were used to pack the remaining 3.0 cm of the column. Decane was used as the representative NAPL, to which an oil-soluble fluorescence tracer was added. The fluorescence tracer was considered as a constituent of the NAPL that readily reacts with ozone. Air and ozone-containing oxygen were used to generate MNB solutions, and injected through the column. In addition, H2O2 was introduced to the O-3-containing MNB (O-3-MNB) solution to investigate the effect of hydroxyl free radicals on the NAPL removal. An ozone gas sparging experiment was also conducted for comparison. After 72 h of O-3-MNB application, a significant mass of n-decane (27.6% of the initial mass applied) was removed from the column. H2O2 injection into the column during O-3-MNB application was effective in increasing the n-decane mass removal by 22%, compared to the O-3-MNB experiment. The rate of NAPL removal during O-3-MNB flushing was significant, although slower than ozone sparging. During O-3-MNB application, fast decay of fluorescence was observed; whereas, during co-injection of H2O2 and O-3-MNB solutions, only a slight change in the fluorescence was observed. This indicates that oxidative degradation of NAPL during H2O2 and O-3-MNB injection takes place only at the NAPL-water interface due to the reactivity of hydroxyl free radical, whereas ozone diffusion into NAPL induced the decay of the fluorescence tracer in the bulk NAPL. The removal characteristics during MNB application and ozone gas sparging were investigated based on the analysis of NAPL using mass spectrophotometer. When O-3-MNB and H2O2 were co-injected, only n-decane was detected in the NAPL; while when O-3-MNB was used for flushing, oxidative products were found in the NAPL. More hydrophilic compounds were found in the NAPL after ozone sparging. This implies different removal mechanisms depending on the kind of oxidation agent, and the state of oxidizing fluid. Based on the findings in this study, the application of O-3-MNB could be a feasible option for cleaning up NAPL-contaminated aquifers.

The effects of surface-tension and/or viscosity changes in groundwater on the remedial performance of air sparging for heterogeneous aquifers were investigated. The study used a one-dimensional (1-D) column and a two-dimensional (2-D) flow-chamber aquifer model. To introduce a heterogeneous setting, the middle part of the model was packed with a finer soil [LKZ, low hydraulic conductivity ( K ) zone]. Fluorescein sodium salt was used at 200 mg/L for all experiments as a surrogate contaminant. For the 1-D column experiments, the rate of fluorescence decay in the LKZ during surfactant-enhanced air sparging (SEAS) was significantly higher than during the standard air sparing (AS) process without additives; the area of fluorescence loss, measured after 17 h of air sparging (including ozone), was double and triple that of the conventional AS process, for SEAS without thickener (SEAS1) and SEAS with thickener (SEAS2), respectively. Experimental results using the 2-D chamber also confirmed the enhanced air intrusion into the LKZ during the SEAS process. The air fluxes through the LKZ increased by 47 and 103% for the SEAS1 and SEAS2 compared to AS, respectively; and 79 and 90% of fluorescence disappeared in the LKZ during ozone injection for SEAS1 and SEAS2, respectively, whereas only 10% disappeared for AS during the 3-h experimental period. The findings of this study indicate that the AS process, at low surface tension and increased groundwater viscosity may be a viable alternative to the conventional AS process for aquifers of heterogeneous hydrogeological formations.

The effect of groundwater viscosity control on the performance of surfactant-enhanced air sparging (SEAS) was investigated using 1- and 2-dimensional (1-D and 2-D) bench-scale physical models. The viscosity of groundwater was controlled by a thickener, sodium carboxymethylcellulose (SCMC), while an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), was used to control the surface tension of groundwater. When resident DI water was displaced with a SCMC solution (500 mg/L), a SDBS solution (200 mg/L), and a solution with both SCMC (500 mg/L) and SDBS (200 mg/L), the air saturation for sand-packed columns achieved by air sparging increased by 9.5%, 128%, and 154%, respectively, (compared to that of the DI water-saturated column). When the resident water contained SCMC, the minimum air pressure necessary for air sparging processes increased, which is considered to be responsible for the increased air saturation. The extent of the sparging influence zone achieved during the air sparging process using the 2-D model was also affected by viscosity control. Larger sparging influence zones (de-saturated zone due to air injection) were observed for the air sparging processes using the 2-D model initially saturated with high-viscosity solutions, than those without a thickener in the aqueous solution. The enhanced air saturations using SCMC for the 1-D air sparging experiment improved the degradative performance of gaseous oxidation agent (ozone) during air sparging, as measured by the disappearance of fluorescence (fluorescein sodium salt). Based on the experimental evidence generated in this study, the addition of a thickener in the aqueous solution prior to air sparging increased the degree of air saturation and the sparging influence zone, and enhanced the remedial potential of SEAS for contaminated aquifers.