Environmentally benign, economical, and effective surfactants and additives are needed in engineering subsurface energy recovery processes. Biosurfactants have some advantages over chemically synthesized surfactants, but the high costs of microbial-biosynthesis limit their applications in subsurface engineering. Here we propose to use naturally occurring biosurfactants contained within Earth's readily available and inexpensive humus deposits for subsurface engineering applications. We collected humus samples of different types from four different regions, and developed a simple method for extracting natural biosurfactant (NBS) using only four common chemicals. The average NBS extraction yields are 16 ± 3% of the raw humus. No significant differences in elemental composition and functional group chemistry were found among the NBS extracted from humus of different origins, suggesting that any humus deposit can be used for NBS extraction. Measurements of interfacial tensions between air-water and supercritical (sc) CO2-water interfaces indicate that the NBS is a highly effective surfactant. NBS has good foaming ability. Preliminary tests with only 0.5 mass % NBS in the aqueous phase (no other additives) yielded scCO2-in-water foams of 83% foam quality. The apparent viscosity of 13 cP measured at a shear rate of 2320 s-1 indicates that much higher viscosities are achievable at lower shear rates. These results suggest that NBS merits further research and development for potential applications in subsurface energy production.

It is commonly true that a diluted colloidal suspension is more stable over time than a concentrated one because dilution reduces collision rates of the particles and therefore delays the formation of aggregates. However, this generalization does not apply for some engineered ligand-coated nanoparticles (NPs). We observed the opposite relationship between stability and concentration of NPs. We tested 4 different types of NPs: CdSe-11-mercaptoundecanoic acid, CdTe-polyelectrolytes, Ag-citrate, and Ag-polyvinylpyrrolidone. The results showed that dilution alone induced aggregation and subsequent sedimentation of the NPs that were originally monodispersed at very high concentrations. Increased dilution caused NPs to progressively become unstable in the suspensions. The extent of the dilution impact on the stability of NPs is different for different types of NPs. We hypothesize that the unavoidable decrease in free ligand concentration in the aqueous phase following dilution causes detachment of ligands from the suspended NP cores. The ligands attached to NP core surfaces must generally approach exchange equilibrium with free ligands in the aqueous phase; therefore, ligand detachment and destabilization are expected consequences of dilution. More studies are necessary to test this hypothesis. Because the stability of NPs determines their physicochemical and kinetic behavior including toxicity, dilution-induced instability needs to be understood to realistically predict the behavior of engineered ligand-coated NPs in aqueous systems. Environ Toxicol Chem 2018;37:1301-1308. © 2018 SETAC.

Wettability is an important factor controlling the displacement of immiscible fluids in porous media and therefore affects the flow and transport of supercritical (sc) CO2 in geologic carbon sequestration. Because few studies have focused on the wettability effect in scCO2-brine flow systems, we experimentally and numerically tested influences of wettability on drainage at the pore network scale. Using a high-pressure micromodel-microscopy system, we performed experiments of scCO2 invasion into brine-saturated water-wet and intermediate-wet micromodels, and recorded the scCO2 invasion morphology under reservoir relevant conditions. We also performed pore-scale numerical simulations to infer 3D details of fluid–fluid displacement processes. During drainage under intermediate-wet conditions, we found higher scCO2 saturation, wider scCO2 fingering, and more compact displacement patterns. The simulation results are qualitatively consistent with the experiments. Through quantitative analyses of the experiments, we found that the reduced wettability decreases the displacement front velocity, promotes non-wetting phase pore-filling events in the longitudinal direction, delays the breakthrough time of invading fluid, and increases the displacement efficiency. Simulated results also show that the fluid–fluid interface area follows a unified power-law relation with scCO2 saturation, and show smaller interface area in intermediate-wet case which suppresses the mass transfer between the phases. These pore-scale results provide insights for the wettability effects on CO2–brine immiscible displacement in geologic carbon sequestration.

How the wettability of pore surfaces affects supercritical (sc) CO2 capillary trapping in geologic carbon sequestration (GCS) is not well understood, and available evidence appears inconsistent. Using a high-pressure micromodel-microscopy system with image analysis, we studied the impact of wettability on scCO2 capillary trapping during short-term brine flooding (80 s, 8–667 pore volumes). Experiments on brine displacing scCO2 were conducted at 8.5 MPa and 45°C in water-wet (static contact angle θ = 20° ± 8°) and intermediate-wet (θ = 94° ± 13°) homogeneous micromodels under four different flow rates (capillary number Ca ranging from 9 × 10−6 to 8 × 10−4) with a total of eight conditions (four replicates for each). Brine invasion processes were recorded and statistical analysis was performed for over 2000 images of scCO2 saturations, and scCO2 cluster characteristics. The trapped scCO2 saturation under intermediate-wet conditions is 15% higher than under water-wet conditions under the slowest flow rate (Ca ∼ 9 × 10−6). Based on the visualization and scCO2 cluster analysis, we show that the scCO2 trapping process in our micromodels is governed by bypass trapping that is enhanced by the larger contact angle. Smaller contact angles enhance cooperative pore filling and widen brine fingers (or channels), leading to smaller volumes of scCO2 being bypassed. Increased flow rates suppress this wettability effect.

Brine-mica interfacial interactions affect both the caprock integrity and the fate and transport of reactive fluids at deep subsurface sites. Phosphate naturally exists at low concentration in subsurface brines, and its concentration can be increased significantly during energy-related engineered subsurface processes. However, our understanding of the influence of phosphate on brine-mica interactions is limited, especially under subsurface conditions. Here, biotite dissolution experiments were conducted without and with phosphate (0.1, 1, and 10 mM) at 95 °C and 102 atm CO₂. Compared to the control, 0.1 mM, and 1 mM phosphate systems, biotite dissolution was four times higher with 10 mM phosphate. Despite the dissolution differences, in all the phosphate systems, phosphate interacted with Al and Fe sites in biotite, forming surface complexation and precipitating as Fe- or Al-bearing minerals on surfaces and in solutions. Consequently, aqueous Fe and Al concentrations became lower with phosphate than in the control experiments. In addition, the biotite basal surfaces became more hydrophilic after reaction with phosphate, even at 0.1 mM, mainly from phosphate adsorption. This study offers new information on how phosphate-containing brine interacts with caprocks and on the consequent wettability changes, results that can benefit current and future energy-related subsurface engineering processes.

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, 17 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.

Diffusion is important in controlling local solute transport and reactions in unsaturated soils and geologic formations. Although it is commonly assumed that thinning of water films controls solute diffusion at low water contents, transport under these conditions is not well understood. We conducted experiments in quartz sands at low volumetric water contents (θ) to quantify ion diffusion within adsorbed films. At the lowest water contents, we employed fixed relative humidities to control water films at nm thicknesses. Diffusion profiles for Rb⁺ and Br^- in unsaturated sand packs were measured with a synchrotron X-ray microprobe, and inverse modeling was used to determine effective diffusion coefficients, D_e, as low as ∼9 × 10^-15 m² s^-1 at θ = 1.0 × 10^-4 m³ m^-3, where the film thickness = 0.9 nm. Given that the diffusion coefficients (D_o) of Rb⁺ and Br^- in bulk water (30 °C) are both ∼2.4 × 10^-9 m² s^-1, we found the impedance factor f = D_e/(θD_o) is equal to 0.03 ± 0.02 at this very low saturation, in agreement with the predicted influence of interface tortuosity (τ_a) for diffusion along grain surfaces. Thus, reduced cross-sectional area (θ) and tortuosity largely accounted for the more than 5 orders of magnitude decrease in D_e relative to D_o as desaturation progressed down to nanoscale films.

Transport from the soil surface to groundwater is commonly mediated through deeper portions of the vadose zone and capillary fringe, where variations in temperature and water saturation strongly influence biogeochemical processes. This technical note describes a sediment column design that allows laboratory simulation of thermal and hydrologic conditions found in many field settings. Temperature control is particularly important because room temperature is not representative of most subsurface environments. A 2.0-m-tall column was capable of simulating profiles with temperatures ranging from 3 to 22°C, encompassing the full range of seasonal temperature variation observed in the deep vadose zone and capillary fringe of a semiarid floodplain in western Colorado. The water table was varied within the lower 0.8-m section of the column, and profiles of water content and matric potential were measured. Vadose zone CO2 collected from depth-distributed gas samplers under representative seasonal conditions reflected the influences of temperature and water table depth on microbial respiration. Thus, realistic subsurface biogeochemical dynamics can be simulated in the laboratory through establishing column profiles that represent seasonal thermal and hydrologic conditions.

Large volumes of water are used for hydraulic fracturing of low permeability shale reservoirs to stimulate gas production, with most of the water remaining unrecovered and distributed in a poorly understood manner within stimulated regions. Because water partitioning into shale pores controls gas release, we measured the water saturation dependence on relative humidity (rh) and capillary pressure (Pc) for imbibition (adsorption) as well as drainage (desorption) on samples of Woodford Shale. Experiments and modeling of water vapor adsorption into shale laminae at rh50.31 demonstrated that long times are needed to characterize equilibrium in larger (5 mm thick) pieces of shales, and yielded effective diffusion coefficients from 9 3 1029 to 3 3 1028 m2 s21, similar in magnitude to the literature values for typical low porosity and low permeability rocks. Most of the experiments, conducted at 508C on crushed shale grains in order to facilitate rapid equilibration, showed significant saturation hysteresis, and that very large Pc ( 1 MPa) are required to drain the shales. These results quantify the severity of the water blocking problem, and suggest that gas production from unconventional reservoirs is largely associated with stimulated regions that have had little or no exposure to injected water. Gravity drainage of water from fractures residing above horizontal wells reconciles gas production in the presence of largely unrecovered injected water, and is discussed in the broader context of unsaturated flow in fractures.