The effect of soil‐particle size on hydrocarbon entrapment near a dynamic water table

The entrapment of residual hydrocarbon globules by water table fluctuations can produce a long‐term contamination threat to groundwater supplies that is difficult to remove. The mobilization of entrapped hydrocarbon globules depends on the balance between capillary and gravitational forces represented by the Bond number. It is important to estimate the potential for hydrocarbon entrapment at a spill site due to its influence on the effectiveness of remediation efforts. The present work focuses on the influence of particle diameter on hydrocarbon entrapment for a typical LNAPL (light nonaqueous‐phase liquid). Laboratory column tests have been conducted using a dual‐beam gamma densitometer to measure saturations of the three phases (water, air, and hydrocarbon). Soltrol 170^®, a solvent manufactured by Phillips 66 Co., is used as the hydrocarbon. Residual saturation of the Soltrol is measured after fluctuations in water table level to establish the distribution and consistency of hydrocarbon entrapment below the water table. Glass particles of nearly uniform size were used to represent a sandy soil. In the experiments, average particle sizes ranged from 210 to 6000 μm. Data were also taken using the synthetic soil matrix approved by the U.S. Environmental Protection Agency (EPA) for contamination studies. Results show that the distribution of trapped LNAPL is quite uniform and that the average residual saturation is about 13% up to a particle diameter of 710 μm. Above this diameter, residual saturation decreases with particle size. The corresponding critical Bond number, determined experimentally, agrees well with the predicted value of 1.6.     

Acknowledgment

In a water wet porous medium, the antecedent moisture content controls the entrapment of LNAPL at low capillary numbers. A two‐phase retention cell study of entrapment was conducted for LNAPL water systems in a carbonate sand. For two different LNAPL water systems, it was found that a linear expression related the residual LNAPL saturation to the antecedent water saturation. The prediction of trapped LNAPL saturation compares favorably to long‐column test data obtained for the same sand. A trapping model was developed, and its predictions were compared to field measurements of trapped LNAPL saturation. Deviations between predicted and measured LNAPL saturations arose when there was a change in the median pore size distribution. In addition, a series of three‐phase (air‐LNAPL‐water) retention cell tests measured the amount of LNAPL that became trapped when the water phase was maintained at a constant saturation during LNAPL withdrawal under a negative pressure head. Under these conditions, the amount of trapped LNAPL was higher than that measured by two‐phase tests at the same water saturation.     

Feasibility of in situ implementation of vibrations to mobilize NAPL ganglia

A growing number of incidents of nonaqueous phase liquid (NAPL) spills in the recent past have warranted development of innovative and cost‐effective remediation technologies. Of particular concern is the entrapment of LNAPL (NAPL lighter than water) in the form of ganglia or blobs near the water table by virtue of strong capillary forces. The residual ganglia are the leftover component after pumping of free product and typically occupy 20 to 60% of the pore space. Mobilization of these ganglia would require unrealistically high hydraulic gradients and is often beyond the scope of pump‐and‐treat processes. This paper deals with the feasibility of in situ implementation of localized vibrations for controlled mobilization and collection of LNAPL ganglia. Specifically, the paper covers three components. First, the principles involved in soil‐water‐NAPL interactions under the influence of vibrations are discussed. The effects of vibrations on a soil‐NAPL‐water medium are postulated in terms of pore structure and relative density changes, changes in the permeability of the medium as a result of the changes in pore structure, and development of cyclic pore pressures. Second, results from bench‐scale experiments are presented that involved vibrating contaminated soils under the simultaneous influence of hydraulic gradients. A bench‐scale model consisting of a vibrator integrated with an injection and pumping system was found to be successful in these experiments. The results from the tests showed that up to 85% removal of ganglia can be achieved using this process. Third, the principles involved in the vibratory mobilization were applied to in situ conditions to develop a methodology to estimate the zone of influence of the process. The analogy between this process and an existing geotechnical process known as vibroflotation is exploited to demonstrate the methodology.     

Behavior of a Viscous LNAPL Under Variable Water Table Conditions

An intermediate-scale experiment in a 1.02-m-long, 0.75-m-high, and 0.05-m-wide flow cell was conducted to investigate the behavior of a viscous LNAPL under variable water table conditions. Two viscous LNAPL volumes (0.4 L) were released, one week apart, from a small source zone on top of the flow cell into a partly saturated, homogenously packed porous medium. Following a redistribution period of 30 days after the second release, the water table was increased 0.5 m in 50 minutes. After the water table rise, viscous LNAPL behavior was monitored for an additional 45 days. Fluid saturation scans were obtained periodically with a fully automated dual-energy gamma radiation system. Results show that both spills follow similar paths downwards. Within two hours after the first LNAPL arrival, the capillary fringe was reduced across the cell by approximately 0.04 m (22%). This reduction is directly related to the decrease in the air-water surface tension from 0.072 to 0.057 N/m.

LNAPL drainage from the unsaturated zone was relatively slow and a considerable residual LNAPL saturation was observed after 30 days of drainage. Most of the mobile LNAPL moved into the capillary fringe during this period. After a rapid 0.5 m water table rise, the LNAPL moved up in a delayed fashion. The LNAPL used the same path upwards as it used coming down during the infiltration phase. After 45 days, the LNAPL had moved up only approximately 0.2 m. Since the LNAPL had only moved up a limited amount, nonwetting fluid entrapment was limited. The experiment was simulated using the STOMP multifluid flow simulator, which includes entrapped and residual LNAPL saturation formation. A comparison indicates that the simulator is able to predict the observed phenomena well, including residual saturation formation in the vadose zone, and limited upward LNAPL movement after the water table rise. The results of this experiment show that viscous mobile LNAPL, subject to variable water table conditions, does not necessarily float on the water table and may not appear in an observation well.     

Numerical Simulations and Long-Column Tests of LNAPL Displacement and Trapping by a Fluctuating Water Table

Long-column laboratory tests were performed to validate improvements to the MOFAT program for simulating LNAPL displacement and entrapment in response to a fluctuating water table. The long-column tests consisted of a fluctuating water table and its subsequent displacement and entrapment of an LNAPL. The modifications of MOFAT include a linear LNAPL trapping estimate and a new scaling technique for the inhibition portion of the fluctuation (water table rise). Improved prediction of the LNAPL trapping was obtained by assuming the amount of LNAPL that is trapped by a rising water table is proportional to the antecedent water content of the porous medium. The pressure-saturation relationship for the air-water drainage system was scaled to estimate the LNAPL-water and air-LNAPL drainage relationships. Scaled inhibition pressure-saturation relationships are improved by incorporating a correction for contact angle hysteresis and surface roughness. The incorporation of these changes into MOFAT led to noticable improvements in the numerical simulation of the experimental data.     

The surface activity of Acinetobacter calcoaceticus sp. 2CA2

The hydrocarbon metabolizing Acinetobacter calcoaceticus sp. 2CA2 reduces the surface tension of the culture broth during growth on liquid hydrocarbons. This activity, which is not evident during growth on soluble substrates, is associated with the whole cells. Removing the cells from the culture broth increases the surface tension of the liquid phase. The cells when resuspended in water result in a dramatic lowering of the surface tension. Acinetobacter sp. 2CA2 tends to partition between the two liquid phases during growth on hydrocarbons. Both the hydrocarbon bound and nonadhering cells are equally surface active. The whole cells are also able to form and stabilize kerosene-water emulsions. This ability is not related to the lowering of the liquid surface or interfacial tension, since both surface active and nonsurface active cells demonstrated the same emulsifying properties. An extracellular lipopeptide produced during growth on hydrocarbons is not surface active but effectively forms and stabilizes kerosene-water emulsions. The cells and extracellular lipoptide are also effective in de-emulsifying surfactant stabilized test emulsions. The lipopeptide product reduced the half-life of a Tween-Span (TS) stabilized kerosene-water emulsion from 650 to 0.4 h at product concentrations of less than 1% (w/v).     

Oil drop size and gas hold-up in an oil–water airlift system with motionless mixers

The degree of emulsification, measured as surface area of oil generated, was studied. The effect of interfacial tension, volume fraction of oil, and power per unit volume on the Sauter mean diameter of the oil drops was determined in an airlift system with motionless mixers. A mathematical expression to predict the Sauter mean diameter was developed using regression techniques. From this equation another equation, which will predict the surface area of oil in terms of the same variables, was derived. The effects of water air surface tension and power per unit volume on the gas hold-up were obtained using similar techniques. The results show that the interfacial tension and the surface tension are important variables when hydrocarbon fermentations are carried out in airlift systems.     

Cell Surface Measurements in Hydrocarbon and Carbohydrate Fermentations

Acinetobacter calcoaceticus was grown in 11-liter batch fermentations with hexadecane or sodium citrate as the sole source of carbon. Surface and interfacial tension measurements of the microbial broth indicated that surface-active compounds were being produced only during growth on the hydrocarbon substrate. Contact angle measurements of an aqueous drop on a smooth lawn of cells in a hexadecane bath indicated a highly hydrophobic surface of the cells in the initial stages of the hydrocarbon fermentation (120° contact angle). At this stage, the entire cell population was bound to the hydrocarbon-aqueous interface. The contact angle dropped rapidly to approximately 45° after 14 h into the fermentation. This coincided with a shift of the cell population to the aqueous phase. Thus, the cells demonstrated more hydrophilic characteristics in the later stages of the fermentation. Contact angles on cells grown on sodium citrate ranged from 18 to 24° throughout the fermentation. The cells appear to be highly hydrophilic during growth on a soluble substrate. From the contact angle and aqueous-hydrocarbon interfacial tension, the surface free energy of the cells was calculated along with the cell-aqueous and cell-hydrocarbon interfacial tension. The results of these measurements were useful in quantitatively evaluating the hydrophobic nature of the cell surface during growth on hydrocarbons and comparing it with the hydrophilic nature of the cell surface during growth on a soluble substrate.     

Prediction of leachate concentrations in petroleum‐contaminated soils

The efficacy of cleanup methods in reducing gasoline contamination at spill sites is typically determined by measuring benzene, toluene, xylene (BTX), and total petroleum hydrocarbon (TPH) concentrations in soil samples. Although these values may provide a direct measurement of soil contamination, they may not be indicative of what is transferred to percolating water. This study addresses this issue by measuring TPH, toluene, m‐ and p‐xylene, and naphthalene levels in gasoline‐contaminated soil columns before and after forced‐air venting and relating these values to the aqueous‐phase concentrations measured when water is percolated through the same columns.

Sandy soils with and without organic matter were packed into glass columns. The soils were brought to residual water and residual gasoline saturations by applying a vacuum to a ceramic pressure plate at the column bottom. Venting was performed by passing clean, moist air through the columns. The columns were subsequently leached under unsaturated conditions.

Soil samples were taken from the bottom of the columns upon completion of the venting or leaching phases of the experiments. Toluene, m‐ and p‐xylene, naphthalene, and TPH values were measured in soil samples extracted with either freon or methanol. Aqueous phase concentrations of these compounds were predicted using measured soil concentrations and either Raoult's law or organic matter‐water and fuel‐water partitioning theory (Boyd and Sun, 1990). The predicted results were compared with measured leachate concentrations from the same columns.

Mole fractions estimated from soil concentrations and TPH values used in Raoult's law gave good predictions of aqueous phase concentrations for compounds that had a high mole fraction in the residual nonaqueous phase liquid (NAPL). For compounds at low concentrations in the residual NAPL, an approach using a distribution coefficient that accounted for both the organic matter and residual NAPL in the soil provided better estimates than those based on Raoult's law.     

Microemulsion‐mediated removal of residual gasoline from soil columns

In situ pumping of micellular solutions of surfactant (S) and cosurfactant (CoS) in water (W) through contaminated soils or aquifers offers potential for enhanced remediation of residual nonaqueous‐phase liquids (NAPLs). Extremely low interfacial tension generated between a W/S/CoS mixture and residual NAPL in soil pores may initially mobilize the NAPL, which is then transported temporarily as a separate phase by immiscible displacement. The NAPL is then solubilized by micro‐emulsification as the W/S/CoS mixture forms a stable W/S/CoS/NAPL micro‐emulsion that undergoes miscible displacement through the pore space. This remediation technique was tested under laboratory conditions by sequentially flushing a saline solution and a W/S/CoS mixture through columns of a sandy soil recently contaminated with residual leaded gasoline (LG). Prior to the flushings, the soil was initially contaminated by applying a W/S/CoS/LG microemulsion. A simple conceptual transport model with kinetic clogging of soil pores adequately described breakthrough curves for gasoline and organolead in the soil columns.     

The dependence of the conductance and lifetime of gramicidin channels on the thickness and tension of lipid bilayers

The lifetimes of channels formed by natural gramicidin and its dimeric analog in monoglyceride lipid bilayers of various compositions were investigated. The bilayer surface tension was altered by changing the length of the monoglycerides' fatty acid chain or the chain length of hydrocarbon solvent by isomerization or saturation of the lipid, by varying the amount of solvent in the bilayer, and by changing the salt composition of the aqueous solutions. The logarithms of mean channel lifetimes were found to be proportional to the surface tension of the membrane irrespective of how the surface tension was changed. In contrast, no simple relationship between channel conductance and surface tension or bilayer thickness was found.     

Composition and Oil-Water Interfacial Tension Studies in Different Vegetable Oils

The interfacial tension is one of the most important fundamental properties and presents crucial impacts throughout vegetable oil production, application and digestion. In this study, composition of vegetable oil including tocopherols, phytosterols, phenolic compounds, phospholipids, fatty acid composition and other constituents were determined. Furthermore, interfacial tension and its relationship with vegetable oil compositions were analyzed. Distribution and profile of composition of vegetable oil were remarkably different. The interfacial tension results showed physical refined vegetable oil exhibited an obviously lower interfacial tension than chemical refined oil attributed to abundant minor compositions. Moreover, the correlation analysis results indicated that phenolic compounds demonstrated the greatest influence on interfacial tension of vegetable oil against water with r = − 0.671, p = 0.009, followed by free fatty acid value, linoleic acid of triglyceride and phospholipids with r = − 0.639, 0.626, − 0.576 and p = 0.014, 0.017 and 0.031, respectively. No significant correlation was found between interfacial tension and other minor compositions. These results contribute to regulating lipid metabolism and evaluating oil quality more scientifically.

     

The isolation of a thermophilic biosurfactant producing Bacillus SP

Summary A thermophilic Bacillus strain has been isolated on a hydrocarbon containing medium and grew at up to 50°C. This strain produced biosurfactant and its 20h old culture broth had low surface and interfacial tension (27–29 and 1.5 mN/m, respectively). It emulsified Kerosene and other hydrocarbons efficiently (E–24 = 95 %) and was able to recover more than 95 % of the residual oil from sandpack columns. Potential uses in oil industries are discussed.     

生物表面活性剂发酵液的组成及表面活性

假单胞菌（Pseudomonas sp.)生长在正烷烃或植物油中,能生产出表面活性物质,分析其发酵液,类脂物和多糖是主要代谢产物,发酵液中表面活性物质主要是糖脂化合物及甘油单脂,发酵液稀释到5%,能将表面张力降到27mN/m,表面性能在广泛pH(2-12),高矿化度溶液中和高温下都非常稳定,发酵液的良好表面性能显示了它在三次采油,土壤处理等领域中应用潜力。     

Dynamic surface tension of natural surfactant extract under superimposed oscillations

Surfactant dysfunction plays a major role in respiratory distress syndrome (RDS). This research seeks to determine whether the use of natural surfactant, Curosurf? (Cheisi Farmaceutici, Parma, Italy), accompanied with pressure oscillations at the level of the alveoli can reduce the surface tension in the lung, thereby making it easier for infants with RDS to maintain the required level of functional residual capacity (FRC) without collapse. To simulate the alveolar environment, dynamic surface tension measurements were performed on a modified pulsating bubble surfactometer (PBS) type device and showed that introducing superimposed oscillations about the tidal volume excursion between 10 and 70 Hz in a surfactant bubble lowers interfacial surface tension below values observed using tidal volume excursion alone. The specific mechanisms responsible for this improvement are yet to be established; however it is believed that one mechanism may be the rapid transient changes in the interfacial area increase the number of interfacial binding sites for surfactant molecules, increasing adsorption and diffusion to the interface, thereby decreasing interfacial surface tension. Existing mathematical models in the literature reproduce trends noticed in experiments in the range of breathing frequencies only. Thus, a modification is introduced to an existing model to both incorporate superimposed pressure oscillations and demonstrate that these may improve the dynamic surface tension in the alveoli.     

Flow‐dependent entrapment of large bioparticles in porous process media

The need for purification of biomolecules extends to larger bioparticles as well. For example, virus purification is required for production of many vaccines and gene delivery vectors, and understanding virus removal in porous media is also important in downstream processing of therapeutic proteins and in purification of water in soils. A convective entrapment mechanism for retention of large bioparticles is discussed here based on retention of such bioparticles in pore constrictions at high enough flow rates, even under non‐binding conditions. A simple equation to predict whether such entrapment is expected to occur in a given system is derived based on a Péclet number that is proportional to the flow rate and to the cube of the bioparticle diameter. To test the theory, adenovirus was spiked onto chromatographic beds. As expected from the theory, under non‐interacting conditions a progressively larger amount of virus becomes trapped with increasing flow rate. The entrapment is reversible upon flow rate reduction, which, within the proposed model, is based on the possibility of diffusive escape from pore constrictions. This mechanism can be exploited for virus purification or removal, and the theory is also consistent with the anecdotal evidence that monoliths and membranes are more difficult to clean than conventional chromatographic beds, especially at high flow rates. Biotechnol. Bioeng. 2009; 104: 127–133 © 2009 Wiley Periodicals, Inc.     

A decision framework for selecting remediation technologies at hydrocarbon‐contaminated sites

A variety of remediation technologies are available to address hydrocarbon contamination, including free product recovery, soil venting, air sparging, groundwater recovery and treatment, and in situ bioremediation. These technologies address hydrocarbon contamination distributed between free, adsorbed, and dissolved phases in both the vadose and saturated zones. Selection of appropriate technologies is dependent on a number of factors, including contaminants, site‐specific characteristics, clean‐up goals, technology feasibility, cost, and regulatory and time requirements. This article describes a decision framework for selecting appropriate remediation technologies at hydrocarbon‐contaminated sites in a structured and tiered manner. Decision modules include (1) site characterization and product recovery; (2) vadosezone treatment: soil venting, bioremediation, and excavation; (3) saturated zone treatment: sparging, bioremediation, groundwater recovery, and excavation; and (4) groundwater treatment: carbon, air stripping, advanced oxidation, and bioreactors. Selection criteria for treatment technologies that address vadose‐ and saturated‐zone soils, as well as recovered groundwater, are described. The decision framework provides a systematic process to formulate solutions to complex problems and documents the rationale for selecting remediation systems designed to achieve closure at hydrocarbon‐contaminated sites.     

Continuous culture of Candida lipolytica on n-hexadecane

Candida lipolytica was grown continuously on n-hexadecane as the main source of carbon. A transient continuous-culture experiment was also conducted to investigate hydrocarbon-limited growth; the hydrocarbon feed flow rate was stopped for several hours and then resumed at a reduced steady-state flow rate. Interfacial tension, Sauter mean diameter, pseudosolubility, fraction of cells in the aqueous phase, oil-phase volume fraction, and cell concentration were measured to characterize the system. The microorganisms appear to utilize both the submicron drops and the microscopic drops. The effects of interfacial tension, pseudosolubility, and unoccupied interfacial area on the kinetics of hydrocarbon fermentation are discussed here. A conceptual model for hydrocarbon uptake is presented and discussed.     

Bench-Scale Production of Biosurfactants and their Potential in Ex-Situ MEOR Application

The fermentative production of biosurfactants by five Bacillus strains in a bench-scale bioreactor and evaluation of biosurfactant-based enhanced oil recovery using sand pack columns were investigated. Adjusting the initial dissolved oxygen to 100% saturation, without any further control and with collection of foam and recycling of biomass, gave higher biosurfactant production. The microorganisms were able to produce biosurfactants, thus reducing the surface tension and interfacial tension to 28 mN/m and 5.8–0.5 mN/m, respectively, in less than 10 hours. The crude surfactant concentration of 0.08–1.1 g/L, and critical micelle concentration (CMC) values of 19.4–39 mg/L, corresponding to the biosurfactants produced by the different Bacillus strains, were observed. The efficiency of crude biosurfactant preparation obtained from Bacillus strains for enhanced oil recovery, by sand pack column studies, revealed it to vary from 30.22–34.19% of the water flood residual oil saturation. The results are indicative of the potential of the strains for the development of ex-situ, microbial-enhanced, oil recovery processes.     

Reservoir Condition Pore-scale Imaging of Multiple Fluid Phases Using X-ray Microtomography

X-ray microtomography was used to image, at a resolution of 6.6 µm, the pore-scale arrangement of residual carbon dioxide ganglia in the pore-space of a carbonate rock at pressures and temperatures representative of typical formations used for CO₂ storage. Chemical equilibrium between the CO₂, brine and rock phases was maintained using a high pressure high temperature reactor, replicating conditions far away from the injection site. Fluid flow was controlled using high pressure high temperature syringe pumps. To maintain representative in-situ conditions within the micro-CT scanner a carbon fiber high pressure micro-CT coreholder was used. Diffusive CO₂ exchange across the confining sleeve from the pore-space of the rock to the confining fluid was prevented by surrounding the core with a triple wrap of aluminum foil. Reconstructed brine contrast was modeled using a polychromatic x-ray source, and brine composition was chosen to maximize the three phase contrast between the two fluids and the rock. Flexible flow lines were used to reduce forces on the sample during image acquisition, potentially causing unwanted sample motion, a major shortcoming in previous techniques. An internal thermocouple, placed directly adjacent to the rock core, coupled with an external flexible heating wrap and a PID controller was used to maintain a constant temperature within the flow cell. Substantial amounts of CO₂ were trapped, with a residual saturation of 0.203 ± 0.013, and the sizes of larger volume ganglia obey power law distributions, consistent with percolation theory.