Interfacial Partitioning Tracer Tests Research Articles

Influence of Sub-CMC Rhamnolipid Flushing on the Mobilization and Solubilization of Residual Dodecane in Saturated Porous Media

The potential of monorhamnolipid (monoRL) biosurfactant to enhance the removal of residual dodecane from a porous medium was investigated under monoRL concentration varying from sub-CMC to hyper-CMC conditions by one-dimension column experiments. In the immiscible displacement experiment, 76% of the total volume of dodecane is removed by flushing of 150 μM monoRL solution. The solubilization of dodecane could be enhanced by rhamnolipid even at monorhamnolipid concentrations as low as 50 μM/L. The higher solubilization concentration (500 μM/L) of monoRL solution results in higher solubilized dodecane concentration (160 μM/L) due to the larger quantity of micelle formation. Compared to solubilization, immiscible displacement, or mobilization, is far more effective in removing residual dodecane. The interfacial partitioning tracer tests (IPTT) method is applied to measure the variation in specific dodecane-water interface areas (Anw). The results showed that the flushing of monoRL increased the Anw from 2.04 to 3.54 cm2/cm3. This investigation implies that low-concentration monorhamnolipid flushing and subsequent micelle solubilization is an economic method to remediate NAPL-contaminated fields.

Characterization of the micro-scale surface roughness effect on immiscible fluids and interfacial areas in porous media using the measurements of interfacial partitioning tracer tests

This study presents a model-based methodology to characterize the surface roughness effect on immiscible fluids in porous media using the measurements obtained with the gas-phase interfacial partitioning tracer test (IPTT). The characterization approach captures how adsorbed wetting film configuration on grain surfaces influences fluid-fluid interfaces in unsaturated porous media. The method establishes a novel representation of surface and interface roughness that delineates the micro-scale fractal nature of grain surfaces and the fluid-surface interactions at these scales. The method was tested using reported experimental data for several soils. The results showed that the methodology was effective for natural porous media comprising a range of physical and geochemical properties. Comparisons between characterized parameters of different media revealed that micro-scale surface roughness was only partially correlated to soil texture properties. Images of the test media obtained with scanning electron microscopy (SEM) illustrates the complexity of micro-scale surface roughness, and its variability among different media. Tests with an organic liquid–water system validated the generalness of surface roughness properties generated by the model. The proposed methodology is anticipated to provide a means to characterize and quantify the effects of surface roughness on fluid-solid interaction and fluid-fluid interfacial area, which are critical to various environmental disciplines.

NAPL-water interfacial area as a function of fluid saturation measured with the interfacial partitioning tracer test method

The presence of organic immiscible liquids such as chlorinated solvents and fuels continues to be a primary source of risk for many hazardous waste sites. In this study, the standard miscible-displacement interfacial partitioning tracer test (IPTT) method was used for the first time to measure NAPL-water interfacial areas for a range of saturations. Multiple measurements were conducted for a natural quartz sand, with tetrachloroethene as the representative NAPL. The interfacial areas increased with decreasing water saturation. The measurements compared well to interfacial areas measured for the same sand with two alternative tracer methods, the mass-distribution batch method and the two-phase flow method. Measurements obtained with all three tracer-based methods exhibit a relatively large degree of variability. Thus, it is important to employ replication when using these methods. In contrast, interfacial areas measured with x-ray microtomography exhibit very small variability. However, the measured interfacial areas do not capture the contribution of surface-roughness to film-associated interfacial area. Each method has associated advantages and disadvantages, and it is important to be cognizant of them during their application.

The Gas-absorption/Chemical-reaction Method for Measuring Air-water Interfacial Area in Natural Porous Media.

The gas-absorption/chemical-reaction (GACR) method used in Chemical Engineering to quantify gas-liquid interfacial area in reactor systems is adapted for the first time to measure the effective air-water interfacial area of natural porous media. Experiments were conducted with the GACR method, and two standard methods (x-ray microtomographic imaging and interfacial partitioning tracer tests) for comparison, using model glass beads and a natural sand. The results of a series of experiments conducted under identical conditions demonstrated that the GACR method exhibited excellent repeatability for maintaining constant water saturation and for measurement of interfacial area (Aia). Coefficients of variation for Aia were 3.5% for the glass beads and 11% for the sand. Estimated maximum interfacial areas (Am) obtained with the GACR method were statistically identical to independent measures of the specific solid surface areas of the media. For example, the Am for the glass beads is 29 (±1) cm-1, compared to 32 (±3), 30 (±2), and 31 (±2) cm-1 determined from geometric calculation, N2/BET measurement, and microtomographic measurement, respectively. This indicates that the method produced accurate measures of interfacial area. Interfacial areas determined with the GACR method were similar to those obtained with the standard methods. For example, Aias of 47 and 44 cm-1 were measured with the GACR and XMT methods, respectively, for the sand at a water saturation of 0.57. The results of the study indicate that the GACR method is a viable alternative for measuring air-water interfacial areas. The method is relatively quick, inexpensive, and requires no specialized instrumentation compared to the standard methods.

Comparison of Fluid-Fluid Interfacial Areas Measured with X-ray Microtomography and Interfacial Partitioning Tracer Tests for the same Samples.

Two different methods are currently used for measuring interfacial areas between immiscible fluids within 3-D porous media, high-resolution microtomographic imaging and interfacial partitioning tracer tests (IPTT). Both methods were used in this study to measure non-wetting/wetting interfacial areas for a natural sand. The microtomographic imaging was conducted on the same packed columns that were used for the IPTTs. This is in contrast to prior studies comparing the two methods, for which in all cases different samples were used for the two methods. In addition, the columns were imaged before and after the IPTTs to evaluate the potential impacts of the tracer solution on fluid configuration and attendant interfacial area. The interfacial areas measured using IPTT are ~5 times larger than the microtomographic-measured values, which is consistent with previous work. Analysis of the image data revealed no significant impact of the tracer solution on NAPL configuration or interfacial area. Other potential sources of error were evaluated, and all were demonstrated to be insignificant. The disparity in measured interfacial areas between the two methods is attributed to the limitation of the microtomography method to characterize interfacial area associated with microscopic surface roughness due to resolution constraints.

The two-phase flow IPTT method for measurement of nonwetting-wetting liquid interfacial areas at higher nonwetting saturations in natural porous media.

Interfacial areas between nonwetting-wetting (NW-W) liquids in natural porous media were measured using a modified version of the interfacial partitioning tracer test (IPTT) method that employed simultaneous two-phase flow conditions, which allowed measurement at NW saturations higher than trapped residual saturation. Measurements were conducted over a range of saturations for a well-sorted quartz sand under three wetting scenarios of primary drainage (PD), secondary imbibition (SI), and secondary drainage (SD). Limited sets of experiments were also conducted for a model glass-bead medium and for a soil. The measured interfacial areas were compared to interfacial areas measured using the standard IPTT method for liquid-liquid systems, which employs residual NW saturations. In addition, the theoretical maximum interfacial areas estimated from the measured data are compared to specific solid surface areas measured with the N2/BET method and estimated based on geometrical calculations for smooth spheres. Interfacial areas increase linearly with decreasing water saturation over the range of saturations employed. The maximum interfacial areas determined for the glass beads, which have no surface roughness, are 32±4 and 36±5 cm-1 for PD and SI cycles, respectively. The values are similar to the geometric specific solid surface area (31±2 cm-1) and the N2/BET solid surface area (28±2 cm-1). The maximum interfacial areas are 274±38, 235±27, and 581±160 cm-1 for the sand for PD, SI, and SD cycles, respectively, and ~7625 cm-1 for the soil for PD and SI. The maximum interfacial areas for the sand and soil are significantly larger than the estimated smooth-sphere specific solid surface areas (107±8 cm-1 and 152±8 cm-1, respectively), but much smaller than the N2/BET solid surface area (1387±92 cm-1 and 55224 cm-1, respectively). The NW-W interfacial areas measured with the two-phase flow method compare well to values measured using the standard IPTT method.

Measuring air–water interfacial area for soils using the mass balance surfactant-tracer method

There are several methods for conducting interfacial partitioning tracer tests to measure air–water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention.

Novel methods for measuring air–water interfacial area in unsaturated porous media

Interfacial partitioning tracer tests (IPTT) are used to measure air–water interfacial area for unsaturated porous media. The standard IPTT method involves conducting tests wherein an aqueous surfactant solution is introduced into a packed column under unsaturated flow conditions. Surfactant-induced drainage has been observed to occur for this method in some cases, which can complicate data analysis and impart uncertainty to the measured values. Two novel alternative approaches for conducting IPTTs are presented herein that are designed in part to prevent surfactant-induced drainage. The two methods are termed the dual-surfactant IPTT (IPTT-DS) and the residual-air IPTT (IPTT-RA). The two methods were used to measure air–water interfacial areas for two natural porous media. System monitoring during the tests revealed no measurable surfactant-induced drainage. The measured interfacial areas compared well to those obtained with the standard IPTT method conducted in such a manner that surfactant-induced drainage was prevented.

Interfacial Partitioning Tracer Test Measurements of Organic-Liquid/Water Interfacial Areas: Application to Soils and the Influence of Surface Roughness

Interfacial areas between an organic immiscible liquid and water were measured for two natural soils using the aqueous-phase interfacial partitioning tracer test method. The measured values were compared to measured values for silica sands compiled from the literature. The data were compared using the maximum specific interfacial area as a system index, which is useful for cases wherein fluid saturations differ. The maximum specific interfacial areas measured for the soils were significantly larger than the values obtained for the sands. The disparity between the values was attributed to the impact of surface roughness on solid surface area and hence film-associated interfacial area. A good correlation was observed between maximum specific interfacial area and specific solid surface area measured with the N(2)/BET method. The correlation may serve as a means by which to estimate maximum specific organic-liquid/water interfacial areas. Interfacial areas measured with the interfacial partitioning tracer method were compared to interfacial areas measured with high-resolution microtomography. Values measured with the former method were consistently larger than those measured with the latter, consistent with the general inability of the microtomography method to characterize roughness-associated surface area.

Comparison of interfacial partitioning tracer test and high‐resolution microtomography measurements of fluid‐fluid interfacial areas for an ideal porous medium

Fluid-fluid interfacial area for porous-media systems can be measured with the aqueous-phase interfacial partitioning tracer test (IPTT) method or with high-resolution microtomography. The results of prior studies have shown that interfacial areas measured with the IPTT method are larger than values measured with microtomography. The observed disparity has been hypothesized to result from the impact of porous-medium surface roughness on film-associated interfacial area, wherein the influence of surface roughness is characterized to some extent by the IPTT method but not by microtomography due to resolution constraints. This hypothesis was tested by using the two methods to measure interfacial area between an organic immiscible liquid and water for an ideal glass-beads medium that has no measurable surface roughness. The tracer tests yielded a mean interfacial area of 2.8 (± 5 cm-1), while microtomography produced an interfacial area of 2.7 (± 2 cm-1). Maximum specific interfacial areas, equivalent to areas normalized by non-wetting fluid volume, were calculated and compared to measures of the specific solid surface area. The normalized interfacial areas were similar to the specific solid surface area calculated using the smooth-sphere assumption, and to the specific solid surface area measured using the N2/BET method. The results presented herein indicate that both the IPTT and microtomography methods provide robust characterization of fluid-fluid interfacial area, and that they are comparable absent the impact of surface roughness.

Synchrotron X‐ray microtomography and interfacial partitioning tracer test measurements of NAPL‐water interfacial areas

Interfacial areas between an immiscible organic liquid (NAPL) and water were measured for two natural porous media using two methods, aqueous-phase interfacial partitioning tracer tests and synchrotron X-ray microtomography. The interfacial areas measured with the tracer tests were similar to previously reported values obtained with the method. The values were, however, significantly larger than those obtained from microtomography. Analysis of microtomography data collected before and after introduction of the interfacial tracer solution indicated that the surfactant tracer had minimal impact on fluid-phase configuration and interfacial areas under conditions associated with typical laboratory application. The disparity between the tracer-test and microtomography values is attributed primarily to the inability of the microtomography method to resolve interfacial area associated with microscopic surface heterogeneity. This hypothesis is consistent with results recently reported for a comparison of microtomographic analysis and interfacial tracer tests conducted for an air-water system. The tracer-test method provides a measure of effective, total (capillary and film) interfacial area, whereas microtomography can be used to determine separately both capillary-associated and film-associated interfacial areas. Both methods appear to provide useful information for given applications. A key to their effective use is recognizing the specific nature of the information provided by each, as well as associated limitations.

Measuring Air−Water Interfacial Areas with X-ray Microtomography and Interfacial Partitioning Tracer Tests

Air-water interfacial areas as a function of water saturation were measured for a sandy, natural porous medium using two methods, aqueous-phase interfacial partitioning tracer tests and synchrotron X-ray microtomography. In addition, interfacial areas measured in a prior study with the gas-phase interfacial partitioning tracer-test method for the same porous medium were included for comparison. For all three methods, total air-water interfacial areas increased with decreasing water saturation. The interfacial areas measured with the tracer-test methods were generally larger than those obtained from microtomography, and the disparity increased as water saturation decreased. The interfacial areas measured by microtomography extrapolated to a value (147 cm(-1)) very similar to the specific solid surface area (151 cm(-1)) calculated using the smooth-sphere assumption, indicating that the method does not characterize the area associated with microscopic surface heterogeneity (surface roughness, microporosity). This is consistent with the method resolution of approximately 12 microm. In contrast, the interfacial areas measured with the gas-phase tracer tests approached the N2/BET measured specific solid surface area (56000 cm(-1)), indicating that this method does characterize the interfacial area associated with microscopic surface heterogeneity. The largest interfacial area measured with the aqueous-phase tracer tests was 224 cm(-1), while the extrapolated maximum interfacial area was approximately 1100 cm(-1). Both of these values are larger than the smooth-sphere specific solid surface area but much smaller than the N2/BET specific solid surface area, which suggests that the method measures a limited portion of the interfacial area associated with microscopic surface heterogeneity. All three methods provide measures of total (capillary + film) interfacial area, a primary difference being that the film-associated area is a smooth-surface equivalent for the microtomography method. An advantage of the microtomography method is the ability to determine explicitly both total and capillary-associated interfacial areas, which is problematic for the tracer-test methods.