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Capillary pressure (Pc) – saturation (Sw) relations are essential for predicting equilibrium and flow of immiscible fluid pairs in soils and deeper geologic formations. In systems that are difficult to measure, behavior is often estimated based on capillary scaling of easily measured Pc–Sw relations (e.g., air-water, and oil-water), yet the reliability of such approximations needs to be examined. In this study, seventeen sets of brine drainage and imbibition curves were measured with air-brine, decane-brine, and supercritical (sc) CO2-brine in homogeneous quartz and carbonate sands, using porous plate systems under ambient (0.1 MPa, 23 ˚C) and reservoir (12.0 MPa, 45 ˚C) conditions. Comparisons between these measurements showed significant differences in residual nonwetting phase saturation, Snw,r. Through applying capillary scaling, changes in interfacial properties were indicated, particularly wettability. With respect to the residual trapping of the nonwetting phases, Snwr, CO2 > Snwr, decane > Snwr, air. Decane-brine and scCO2-brine Pc–Sw curves deviated significantly from predictions assuming hydrophilic interactions. Moreover, neither the scaled capillary behavior nor Snw,r for scCO2-brine were well represented by decane-brine, apparently because of differences in wettability and viscosities, indicating limitations for using decane (and other organic liquids) as a surrogate fluid in studies intended to apply to geological carbon sequestration. Thus, challenges remain in applying scaling for predicting capillary trapping and multiphase displacement processes across such diverse fields as vadose zone hydrology, enhanced oil recovery, and geologic carbon sequestration. This article is protected by copyright. All rights reserved.

The current ambiguity on wettability of minerals in CO2–brine systems under the geological CO2 sequestration (GCS) reservoir conditions imparts the greatest uncertainty in predicting capillary behavior controlling safe-storage of CO2. To address this issue we conducted a series of experiments using muscovite as a representative of common aluminosilicate minerals. Based on new experimental results we identified several possible causes of the ambiguity problem in contact angle (CA) measurements. We also found that reaction with water-saturated supercritical (sc) CO2 (but not with scN2) phase severely roughened the muscovite surfaces, largely increased CA hysteresis and CO2 adhesion. Although some methodological influences on contact angle uncertainty can be reduced, the high surface-energy of clean and pristine aluminosilicate minerals have strong tendency to adsorb oppositely changed molecules and particles to reduce their surface energy, resulting in less reproducible CA values. Giving the fact that such clean and pristine mineral surfaces do not exist in real reservoirs, our future investigations shall focus on improving understanding of the effect of long-term CO2–mineral–brine reactions on reservoir wettability under realistic reservoir geochemical conditions.

Many aquifers contaminated by U(VI)-containing acidic plumes are composed predominantly of quartz-sand sediments. The F-Area of the Savannah River Site (SRS) in South Carolina (USA) is an example. To predict U(VI) mobility and natural attenuation, we conducted U(VI) adsorption experiments using the F-Area plume sediments and reference quartz, goethite, and kaolinite. The sediments are composed of ∼96% quartz-sand and 3-4% fine fractions of kaolinite and goethite. We developed a new humic acid adsorption method for determining the relative surface area abundances of goethite and kaolinite in the fine fractions. This method is expected to be applicable to many other binary mineral pairs, and allows successful application of the component additivity (CA) approach based surface complexation modeling (SCM) at the SRS F-Area and other similar aquifers. Our experimental results indicate that quartz has stronger U(VI) adsorption ability per unit surface area than goethite and kaolinite at pH ≤ 4.0. Our modeling results indicate that the binary (goethite/kaolinite) CA-SCM under-predicts U(VI) adsorption to the quartz-sand dominated sediments at pH ≤ 4.0. The new ternary (quartz/goethite/kaolinite) CA-SCM provides excellent predictions. The contributions of quartz-sand, kaolinite, and goethite to U(VI) adsorption and the potential influences of dissolved Al, Si, and Fe are also discussed.

© 2016 American Chemical Society. The wettability of rocks and minerals significantly affects the safety and efficiency of energy-related subsurface operations. Salinity is an important controlling factor in terms of wettability but has received limited attention. We studied the effects of salinity-induced chemical reactions on biotite's wettability changes under relevant subsurface conditions. Biotite was reacted at 95 °C and 102 atm of CO2for 70 h in solutions with salinities of 0, 0.1, 0.5, and 1.0 M NaCl. Then, static and dynamic water contact angles on reacted biotite basal surfaces were measured using a captive drop method. As a result of enhanced biotite dissolution at higher salinities, increased roughness, more negatively charged surfaces, and higher densities of hydroxyl groups on the biotite surfaces made biotite basal surface more hydrophilic. These results provide new information about the interplay of chemical reactions and wettability alterations of minerals, providing a better understanding of CO2transport in subsurface environments.

Wettability of reservoir mineral surfaces is a critical factor controlling CO2 mobility, trapping, and safe-storage in geological carbon sequestration. Although recent studies have begun to show that wettability of some minerals can change in the presence of supercritical CO2 (scCO2), different laboratories have reported significantly different wetting behavior. We studied wettability alteration of silica in CO2–brine systems through measuring equilibrium water contact angles under wide ranges of pressures (0.1 to 25 MPa) and ionic strengths (0 to 5.0 M NaCl), at 45 °C. Using two independent approaches for each of the experiments, we found the following: (1) Equilibrium water contact angles on silica increased up to 17.6° ± 2.0° as a result of reactions with scCO2. This increase occurred primarily within the pressure range 7–10 MPa, and the contact angles remain nearly constant at pressure greater than 10 MPa. (2) The contact angle increased with ionic strength nearly linearly, with a net increase of 19.6...

Comprehensive understanding of the transport and deposition of engineered nanoparticles (NPs) in subsurface is required to assess their potential negative impact on the environment. We studied the deposition behavior of functionalized quantum dot (QD) NPs (CdTe) in different types of sands (Accusand, ultrapure quartz, and iron-coated sand) at various solution ionic strengths (IS). The observed transport behavior in ultrapure quartz and iron-coated sand was consistent with conventional colloid deposition theories. However, our results from the Accusand column showed that deposition was minimal at the lowest IS (1 mM) and increased significantly as the IS increased. The effluent breakthrough occurred with a delay, followed by a rapid rise to the maximum normalized concentration of unity. Negligible deposition in the column packed with ultrapure quartz sand (100 mM) and Accusand (1 mM) rules out the effect of straining and suggests the importance of surface charge heterogeneity in QD deposition in Accusand at higher IS. Data analyses further show that only a small fraction of sand surface area contributed in QD deposition even at the highest IS (100 mM) tested. The observed delay in breakthrough curves of QDs was attributed to the fast diffusive mass transfer rate of QDs from bulk solution to the sand surface and QD mass transfer on the solid phase. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis were used to examine the morphology and elemental composition of sand grains. It was observed that there were regions on the sand covered with layers of clay particles. EDX spectra collected from these regions revealed that Si and Al were the major elements suggesting that the clay particles were kaolinite. Additional batch experiments using gold NPs and SEM analysis were performed and it was observed that the gold NPs were only deposited on clay particles originally on the Accusand surface. After removing the clays from the sand surface, we observed negligible QD deposition even at 100 mM IS. We proposed that nanoscale charge heterogeneities on clay particles on Accusand surface played a key role in QD deposition. It was shown that the value of solution IS determined the extent to which the local heterogeneities participated in particle deposition.

The ambiguity of contact angle experimental measurements due to surface chemistry changes resulted from sample contamination and/or the degrees of reaction with supercritical CO2 has resulted in great difficulties to precisely understand the wetting behavior of CO2 under the geological carbon sequestration (GCS) conditions. In this study, water contact angles on quartz surface under GCS conditions were investigated through the combined experimental and molecular dynamics simulation (MDS) methods. The experimental results show that water contact angles increases as ionic strength increases. The effects of pressure and temperature are very weak. The dependence of ionic strength, pressure and temperature is same for monovalent and divalent ions solutions. In the MDS, a hydroxylated quartz surface was used as the base point. A good agreement between the MDS and experimental results were obtained. Using the MDS method, a clean mineral surface with a desired surface chemistry can be constructed, which is difficult in experiments. So by comparing MDS and experimental results, the mechanisms of the reservoir wettability can be better understood. Further investigation can be made on quartz surface with different functional groups to better understand wettability alteration caused by contamination and/or CO2 reaction.

Uranium contamination of soils and sediments often originates from acidic or alkaline waste sources, with diffusion being a major transport mechanism. Measurements of U(VI) diffusion from initially pH 2 and pH 11 solutions into a slightly alkaline Altamont soil and a neutral Oak Ridge soil were obtained through monitoring uptake from boundary reservoirs and from U concentration profiles within soil columns. The soils provided pH buffering, resulting in diffusion at nearly constant pH. Micro X-ray absorption near edge structure spectra confirmed that U remained in U(VI) forms in all soils. Time trends of U(VI) depletion from reservoirs and U(VI) concentration profiles within soil columns yielded Kdvalues consistent with those determined in batch tests at similar concentrations (approximately 1 mM) and much lower than values for sorption at much lower concentrations (nM to microM). These results show that U(VI) transport at high concentrations can be relatively fast at non-neutral pH, with negligible surface diffusion, because of weak sorption.

The high stability of calcium uranyl carbonate complexes in the circumneutral pH range has a strong impact on U(VI) sorption in calcareous soils. To quantify this influence, sorption of U(VI) to soils in the presence of naturally occurring calcium carbonate was investigated by conducting batch experiments in which either U(VI) concentration or solution pH was varied. Two soils containing different calcium carbonate concentrations were selected, one from Oak Ridge, TN, and another from Altamont Pass, CA. The results show that the presence of calcium carbonate in soils strongly affects U(VI) sorption. Higher concentrations of soil calcium carbonate lead to a pronounced suppression of the pH-dependent sorption curve in the neutral pH range because of the formation of a very stable neutral complex of calcium uranyl carbonate in solution. A surface complexation model considering both strong and weak sites for ferrihydrite and ionizable hydroxyl sites for clay minerals was compared with experimental results, and U(VI) binding parameters were reasonably estimated. Fair agreement was found between the model predictions and sorption data, which span a wide range of U(VI) concentrations and pH. The results also show that appropriate solution-to-solid ratios need to be used when measuring distribution coefficients in calcareous soils to avoid complete CaCO3 dissolution and consequent dilution of calcium uranyl carbonate complexes.

Recent studies have shown how water films at near-zero matric potentials on fracture surfaces could permit fast flow in unsaturated fractures. The present work is aimed at delineating the ranges of conditions necessary to permit film flow. The approximate matric potential needed to permit thickening of water films on fracture surfaces was estimated through correlating air-entry matric potentials and permeabilities for a wide range of porous media. An upper matric potential limit, associated with saturating the fracture, was related to the fracture aperture. These two limits, one dependent on matrix permeability and the other on fracture aperture, delineate the matric potential range within which thick water films develop on fracture surfaces. Rocks with matrix permeabilities less than ∼10−14 m2, and fractures with apertures greater than ∼30 μm permit some matric potential range over which thick water films can form. Highly transmissive films can develop on fracture surfaces only under near-zero matric and pressure potentials.

The distribution of metal contaminants such as chromium in soils can be strongly localized by transport limitations and redox gradients within soil aggregates. Measurements of Cr(VI) diffusion and reduction to Cr(III) were obtained in soil columns representing transects into soil aggregates in order to quantify influences of organic carbon (OC) and redox potentials on Cr transport distances and microbial community composition. Shifts in characteristic redox potentials, and the extent of Cr(VI) reduction to Cr(III) were related to OC availability. Depth profiles of Cr(VI, III) obtained with micro X-ray absorption near edge structure (micro-XANES) spectroscopy reflected interdependent effects of diffusion and spatially dependent redox potentials on reduction kinetics and microbial community composition. Shallow diffusion depths (2-10 mm) and very sharply terminated diffusion fronts in columns amended with OC (80 and 800 ppm) reflected rapid increases in Cr reduction kinetics over very short (mm) distances. These results suggest that Cr contamination in soils can be restricted to the outsides of soil aggregates due to localized transport and rapid reduction and that bulk sample characterization is inadequate for understanding the controlling biogeochemical processes.

Although fractures in rock are well recognized as pathways for fast percolation of water, processes which permit fast flow along unsaturated fracture pathways remain to be identified and understood. Earlier aperture-based models of flow in partially saturated fractures permit fast flow only through a continuous network of locally saturated segments. Film flow was recently identified as a mechanism capable of sustaining fast flow along truly unsaturated fractures when the matric potential is very close to zero. Another mechanism for fast flow along unsaturated fractures is introduced in this study, “surface-zone flow,” which can be important when the permeability of the rock along fractures (fracture skin) is significantly greater than that of the bulk rock matrix. In such systems the fracture surface zone provides low resistance pathways through which fast flow (relative to the bulk matrix rock) can occur, even when the fractures are at very low water saturation. Initial experimental tests of surface-zone fast flow were performed. Surface-zone fast imbibition of water was measured on a welded tuff and a rhyolite. However, because (1) imbibition rates are also strongly influenced by rock wettability, (2) these initially air-dry rocks exhibited finite contact angles upon exposure to water, and (3) we lack methods to reliably measure permeabilities of thin regions on rock surfaces, quantification of permeability contrasts was not possible in these initial tests.

A method was developed for fabricating transparent glass casts of fractured rock pairs. These glass casts provide reproduction of surface topography and roughness of natural fractures, optical clarity, and representative wettabilities of mineral surfaces. The glass casts are an improved tool for studying flow and transport in fractures compared to previous approaches. The surface of a clean glass fracture has a contact angle near zero, and more importantly, the surface wettability can be intentionally altered with chemical treatment. Glass casts of rock fracture surfaces may be used for visually and quantitatively studying various physical, chemical, and microbial processes occurring in rock fractures, especially when multiple fluid phases are involved.

Quantification of surface excesses of colloidal particles at gas-liquid interfaces under environmentally relevant conditions has not previously been reported, despite its importance in understanding and predicting partitioning, transport, and transformations of colloids and other organic and metal species complexed onto colloids in many natural environments and engineered systems. In this study, the authors developed a bubble column method for measuring partition coefficients of colloids at air-water interfaces. The method was validated by comparing the adsorption isotherm constant for a surfactant measured using the authors` method with that determined from conventional surface tension measurements and the Gibbs absorption equation. The first measured partition coefficients of kaolinite and humic colloids at the air-water interfaces are reported. The bubble column method can also be used to identify surface exclusion of colloids at the air-water interface. By extension, this method will permit quantification of surface activities of a wide range of inorganic, organic, and microbial colloids as well as molecular species complexed onto colloids.

A film-straining theory is introduced, which proposes that transport of suspended colloids can be retarded due to physical restrictions imposed by thin water films in partially saturated porous media. A quantitative, mechanistic model is provided to predict the film-straining efficiency. In this model, the concepts of “critical matric potential” and “critical saturation” are introduced, at which thick film interconnections between pendular rings are broken and film straining begins to become effective. The modeled magnitude of colloid transport through water films depends on the ratio of colloid size to film thickness and on flow velocity. Effective penetration of hydrophilic colloids through unsaturated porous media is predicted when a system is above the critical saturation value. For colloids smaller than the thickness of adsorbed thin water films, the model predicts that colloids can still be efficiently transported, even when the system matric potential and saturation are lower than their critical va...

This study shows that hydraulic properties of individual fracture surfaces can be meaningfully defined and measured, and that water film flow is a mechanism contributing to fast, unsaturated flow in fractures. The hydraulic conductivity of an unconfined block of Bishop Tuff was measured over a range of near-zero matric potentials, where differences between hydraulic conductivities obtained without and with wax sealing of its lateral sides allowed isolation of film flow effects. Tensiometer and flux measurements showed that surface film flow in this system was significant for matric potentials greater (more positive) than about −250 Pa. In this range the average film thickness was shown to be potential dependent and proportional to the observed enhanced hydraulic conductivity. Measured average surface film thicknesses ranged from 2 to 70 μm, with average film velocities in the range of 2 to 40 m d−1 (about 103 times faster than that of the pore water under unit gradient saturated flow). Our experiments demonstrate that hydraulic properties of macroscopic surfaces of porous media are quantifiable, related to surface roughness, and potentially important in the flow of water in vadose environments. This study further shows that contrary to existing conceptual models, unsaturated flow in fractures cannot generally be predicted solely on the basis of aperture distribution information. The high velocities of these surface films suggest that film flow can be an important mechanism contributing to fast flow in unsaturated fractures and macropores, especially in media characterized by low-permeability matrix and along regions of convergent flow in partially saturated fractures.

Recent studies by [Crist et al. (2004)][1]([2005][2]) attempted to provide pore-scale insights into mechanisms responsible for controlling colloid transport in unsaturated porous media. However, their key observation of colloids being trapped at air–water–solid (AWS) contact lines relied on

Numerous previous studies of bacterial transport in groundwaters and to deep aquifers and sediments have either neglected, or regarded as insignificant, the potential contribution of bacterial sedimentation. This study examines the potential significance of sedimentation as a mechanism for bacterial transport. A simple model is developed to predict the behavior of particles (bacterial or inorganic colloids) sedimenting through granular porous media under hydrostatic conditions. The model indicates that tortuosity-limited sedimentation velocities through porous media consisting of large, well-rounded grains can proceed at velocities close to (≈90% that of) free sedimentation in water columns when particle-grain interactions involve only tortuosity. The assumption of neutral buoyancy of bacteria was demonstrated to be invalid through buoyant density measurements on 25 subsurface bacterial strains (using Percoll density gradient centrifugation). An average buoyant density of 1.088 Mg m−3 was obtained (range from 1.040 to 1.121 Mg m−3). The two nonmotile bacterial strains selected for sedimentation experiments were Arthrobacter globiformis B672 (isolated from the Middendorf aquifer, 259-m depth), and OYS3, a streptomycin-resistant strain isolated from shallow groundwaters at Oyster, Virginia. All experiments were carried out under nongrowth conditions. Stokes' law sedimentation velocities for the two bacterial strains calculated from measurements of buoyant densities and characteristic sizes were 5.8 and 40 mm d−1, respectively. Direct measurements of free sedimentation of Arthrobacter B672 and OYS3 through water columns (21°C) yielded median velocities of 7.1 and 42 mm d−1, respectively, in good agreement with Stokes' law calculations. The Arthrobacter B672 and OYS3 strains sedimented through saturated sand columns (quartz sand, 300–420 μm diameter) under hydrostatic conditions at median velocities of 7 and 17 mm d−1. Thus the sedimentation model is consistent with sand column observations on Arthrobacter B672 and too simplistic in the case of OYS3. Bacterial breakthrough by sedimentation exhibited trends consistent with first-order attenuation with distance. Bacterial deposition coefficients for this first-order model were in the range of 0.008–0.012 mm−1. Surface physical-chemical interactions, grain and pore size distributions, and grain surface microtopography can be very important in controlling the effectiveness of bacterial sedimentation as a transport mechanism. This research suggested that if timescales are sufficiently long, spanning many generations, sedimentation can become a significant mechanism for bacterial transport.

The mobility of an acidic uranium waste plume in the F-Area of Savannah River Site is of great concern. In order to understand and predict uranium mobility, U(VI) adsorption experiments were performed as a function of pH using background F-Area aquifer sediments and reference goethite and kaolinite (major reactive phases of F-Area sediments), and a component-additivity (CA) based surface complexation model (SCM) was developed. Our experimental results indicate that the fine fractions (≤45 μm) in sediments control U(VI) adsorption due to their large surface area, although the quartz sands show a stronger adsorption ability per unit surface area than the fine fractions at pH5.0. Kaolinite is a more important sorbent for U(VI) at pH4.0, while goethite plays a major role at pH4.0. Our CA model combines an existing U(VI) SCM for goethite and a modified U(VI) SCM for kaolinite along with estimated relative surface area abundances of these component minerals. The modeling approach successfully predicts U(VI) adsorption behavior by the background F-Area sediments. The model suggests that exchange sites on kaolinite dominate U(VI) adsorption at pH4.0, goethite and kaolinite edge sites cocontribute to U(VI) adsorption at pH 4.0-6.0, and goethite dominates U(VI) adsorption at pH6.0.

Highly saline and caustic tank waste solutions containing radionuclides and toxic metals have leaked into sediments at U.S. Department of Energy (DOE) facilities such as the Hanford Site (Washington state). Colloid transport is frequently invoked to explain migration of radionuclides and metals in the subsurface. To understand colloid formation during interactions between highly reactive fluids and sediments and its impact on contaminant transport, we simulated tank waste solution (TWS) leakage processes in laboratory columns at ambient and elevated (70 degrees C) temperatures. We found that maximum formation of mobile colloids occurred at the plume fronts (hundreds to thousands times higher than within the plume bodies or during later leaching). Concentrations of suspended solids were as high as 3 mass %, and their particle sizes ranged from tens of nanometers to a few micrometers. Calcium carbonate is always one of the dominant phases of the plume front colloids, while the other phases varied with solution pH and temperature. During infiltration of the leaked high-Na+ waste solution, rapid and completed Na+ replacement of exchangeable Ca2+ and Mg2+ from the sediment caused accumulation of these divalent cations at the moving plume front. Precipitation of supersaturated Ca2+/Mg2+-bearing minerals caused dramatic pH reduction atthe plume front. In turn, the reduced pH caused precipitation of other minerals. This understanding can help predict the behavior of contaminant trace elements carried by the tank waste solutions and could not have been obtained through conventional batch studies.

[1] Hysteresis in the relation between water saturation and matric potential is generally regarded as a basic aspect of unsaturated porous media. However, the nature of an upper length scale limit for saturation hysteresis has not been previously addressed. Since hysteresis depends on whether or not capillary rise occurs at the grain scale, this criterion was used to predict required combinations of grain size, surface tension, fluid-fluid density differences, and acceleration in monodisperse systems. The Haines number (Ha), composed of the aforementioned variables, is proposed as a dimensionless number useful for separating hysteretic (Ha 15) behavior. Vanishing of hysteresis was predicted to occur for grain sizes greater than 10.4 ± 0.5 mm, for water-air systems under the acceleration of ordinary gravity, based on Miller-Miller scaling and Haines' original model for hysteresis. Disappearance of hysteresis was tested through measurements of drainage and wetting curves of sands and gravels and occurs between grain sizes of 10 and 14 mm (standard conditions). The influence of surface tension was tested through measurements of moisture retention in 7 mm gravel, without and with a surfactant (sodium dodecylbenzenesulfonate (SDBS)). The ordinary water system (Ha = 7) exhibited hysteresis, while the SDBS system (Ha = 18) did not. The experiments completed in this study indicate that hysteresis in moisture retention relations has an upper limit at Ha = 16 ± 2 and show that hysteresis is not a fundamental feature of unsaturated porous media.

At the Hanford Site in Washington State, the pH values of contaminant plumes resulting from leaking of initially highly alkaline-saline radioactive waste solutions into the subsurface are now found to be substantially neutralized. However, the nature of plume pH neutralization has not previously been understood. As a master geochemical variable, pH needs to be understood in order to predict the fate and transport of contaminants carried by the waste plumes. Through this laboratory study, we found that the plume pH values spanned a broad range from 14 (within the near-source region) down to the value of 7 (lower than the pH value of the initial soil solution) while the plume was still connected to an actively leaking source. We defined two zones within a plume: the silicate dissolution zone (SDZ, pH 14-10) and the neutralized zone (NZ, pH 10-7). Quartz dissolution at elevated temperature and precipitation of secondary silicates (including sodium metasilicate, cancrinite, and zeolites) are the key reactions responsible for the pH neutralization within the SDZ. The rapid and thorough cation exchange of Na + replacing Ca 2+ /Mg 2+ , combined with transport, resulted in a dynamic Ca 2+ /Mg 2+ -enriched plume front. Subsequent precipitation of calcite, sodium silicate, and possibly talc led to dramatically reduced pH within the plume front and the neutralized zone. During aging (after the plume source became inactive), continued quartz dissolution and the secondary silicate precipitation drove the pH value lower, toward pH 11 at equilibrium within the SDZ, whereas the pH values in the NZ remained relatively unchanged with time. A pH profile of 11 from the plume source to pH 7 at the plume front is expected for a historical plume. This laboratory-based study provided realistic plume pH profiles (consistent with that measured from borehole samples) and identified underlying mechanisms responsible for pH evolution.

Although gravels comprise large portions of some vadose zones, their unsaturated hydraulic properties have received relatively little attention. This study examines moisture retention relations in the 2- and 6-mm size fractions of gravels from the Hanford formation vadose zone (Washington State). Understanding flow and transport within this formation is important because parts of it have become contaminated by leakage of radioactive wastes at the Hanford Site. Moisture retention relations were obtained for a very wide energy range, with attention to water retained in intragranular pores and along grain surfaces. External surfaces of these gravels have root mean-squared roughnesses (rmsr) in the micrometer range, with sparsely distributed deep (hundreds of micrometers) pits. Water films on these external surfaces are volumetrically insignificant at matric potentials less than about −2 kPa. Residual water in these gravels occurs in intragranular pores, accounts for about 10% of the total porosity, and is effectively hydraulically immobile. The intragranular domain in Hanford gravels also has a large specific surface area of about 11 m 2 g −1 . Thus, exchanges of solutes (including contaminants) between the intragranular domain of Hanford gravels and their immediate surrounding are significant and diffusion limited.

Uranium(VI) sorption onto a soil collected at the Melton Branch Watershed (Oak Ridge National Laboratory, TN) is strongly influenced by the pH of the soil solution and, to a lesser extent, by the presence of calcium, suggesting specific chemical interactions between U(VI) and the soil matrix. Batch experiments designed to evaluate factors controlling desorption indicate that two anionic surfactants, AOK and T77, at concentrations ranging from 60 to 200 mM, are most suitable for U(VI) removal from acidic soils such as the Oak Ridge sediment. These surfactants are very efficient solubilizing agents at low uranium concentrations: ca. 100% U(VI) removal for [U(VI)] o,sorbed = 10 -6 mol kg -1 . At greater uranium concentrations (e.g., [U(VI)] o,serbed = ca. 10 -5 mol kg -1 ), the desorption efficiency of the surfactant solutions increases with an increase in surfactant concentration and reaches a plateau of 75 to 80% of the U(VI) initially sorbed. The most probable mechanisms responsible for U(VI) desorption include cation exchange in the electric double layer surrounding the micelles and, to a lesser extent, dissolution of the soil matrix. Limitations associated with the surfactant treatment include loss of surfactants onto the soil (sorption) and greater affinity between U(VI) and the soil matrix at large soil to liquid ratios. Parallel experiments with H 2 SO 4 and carbonate-bicarbonate (CB) solutions indicate that these more conventional methods suffer from strong matrix dissolution with the acid and reduced desorption efficiency with CB due to the buffering capacity of the acidic soil.

In this article, a new mechanism influencing the transport of microorganisms through unsaturated porous media is examined, and a new method for directly visualizing bacterial behavior within a porous medium under controlled chemical and flow conditions is introduced. Resting cells of hydrophilic and relatively hydrophobic bacterial strains isolated from groundwater were used as model microorganisms. The degree of hydrophobicity was determined by contact-angle measurements. Glass micromodels allowed the direct observation of bacterial behavior on a pore scale, and three types of sand columns with different gas saturations provided quantitative measurements of the observed phenomena on a porous medium scale. The reproducibility of each break-through curve was established in three to five repeated experiments. The data collected from the column experiments can be explained by phenomena directly observed in the micromodel experiments. The retention rate of bacteria is proportional to the gas saturation in porous media because of the preferential sorption of bacteria onto the gas-water interface over the solid-water interface. The degree of sorption is controlled mainly by cell surface hydrophobicity under the simulated groundwater conditions because of hydrophobic forces between the organisms and the interfaces. The sorption onto the gas-water interface is essentially irreversible because of capillary forces. This preferential and irreversible sorption at the gas-water interface strongly influences the movement and spatial distribution of microorganisms.