Subsurface Flow and Transport Publications

2013

Miller EA, TA White, BS McDonald, and A Seifert. 2013. "Phase Contrast X-ray Imaging Signatures for Security Applications." IEEE Transactions on Nuclear Science 60(1):416-422. doi:10.1109/TNS.2012.2227803 Abstract Abstract: Differential phase contrast imaging with a grating interferometer is a promising new radiographic technique providing three distinct contrast mechanisms - absorption, phase, and scatter (or dark field) - using a conventional x-ray tube source. We investigate the signatures available in these three contrast mechanisms with attention towards potential security applications. We find that the scatter mode in particular is sensitive to textured materials, enabling lowered detection limits than absorption for materials such as powders. We investigate the length scales to which our imaging system is sensitive.
Schaef HT, BP McGrail, JS Loring, ME Bowden, BW Arey, and KM Rosso. 2013. "Forsterite [Mg2SiO4)] Carbonation in Wet Supercritical CO2: An in situ High Pressure X-Ray Diffraction Study." Environmental Science & Technology 47(1):174-181. doi:10.1021/es301126f Abstract Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous carbonate phase as well as the formation of a thin liquid-like water layer on the forsterite surface. The presence of this water film appears to be critical for the mineral carbonation of forsterite exposed to water bearing scCO2. In contrast, our prior studies with the mineral brucite [Mg(OH)2] showed extensive carbonation in the absence of a condensed water layer on the mineral surface. The contrasts in reaction rate and products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to help enable better predictions of the long term fate of geologically stored CO2.
Wang Y, C Zhang, N Wei, M Oostrom, TW Wietsma, X Li, and AHR Bonneville. 2013. "Experimental study of crossover from capillary to viscous fingering for supercritical CO2 - water displacement in a homogeneous pore network." Environmental Science & Technology 47(1):212-218. doi:10.1021/es3014503 Abstract Carbon sequestration in saline aquifers involves displacing resident brine from the pore space by supercritical CO2 (scCO2). The displacement process is considered unstable due to the unfavorable viscosity ratio (logM < 0). The unstable mechanisms that affect scCO2 - water displacement under reservoir conditions (i.e., 41 °C, 9 MPa) were investigated in a homogeneous micromodel. A wide range of injection rates (logCa = -7.61~-4.73) was studied in two sets of experiments: discontinuous-rate injection, where the micromodel was first cleaned and saturated with water before each injection rate was imposed, and continuous-rate injection, where the rate was increased after quasi-steady conditions were reached for a certain rate. For the discontinuous-rate experiments, capillary fingering and viscous fingering are the dominant mechanisms for low (logCa <= -6.61) and high injection rates (logCa >= -5.21), respectively. Crossover from capillary to viscous fingering was observed for logCa = -5.91~-5.21, resulting in a large decrease in scCO2 saturation. The discontinuous-rate experimental results confirmed the decrease in nonwetting fluid saturation during crossover from capillary to viscous fingering predicted by numerical simulations by Lenormand et al. (1988).1 Capillary fingering was the only mechanism that dominates all injection rates in the continuous-rate experiment, and resulted in monotonic increase in scCO2 saturation.
Turcu RVF, DW Hoyt, KM Rosso, JA Sears, Jr, JS Loring, AR Felmy, and JZ Hu. 2013. "Rotor Design for High Pressure Magic Angle Spinning Nuclear Magnetic Resonance." Journal of Magnetic Resonance 226:64-69. doi:10.1016/j.jmr.2012.08.009 Abstract High pressure magic angle spinning (MAS) nuclear magnetic resonance (NMR) with a sample spinning rate exceeding 2.1 kHz and pressure greater than 165 bar has never been realized. In this work, a new sample cell design is reported, suitable for constructing cells of different sizes. Using a 7.5 mm high pressure MAS rotor as an example, internal pressure as high as 200 bar at a sample spinning rate of 6 kHz is achieved. The new high pressure MAS rotor is re-usable and compatible with most commercial NMR set-ups, exhibiting low 1H and 13C NMR background and offering maximal NMR sensitivity. As an example of its many possible applications, this new capability is applied to determine reaction products associated with the carbonation reaction of a natural mineral, antigorite ((Mg,Fe2+)3Si2O5(OH)4), in contact with liquid water in water-saturated supercritical CO2 (scCO2) at 150 bar and 50 C. This mineral is relevant to the deep geologic disposal of CO2, but its iron content results in too many sample spinning sidebands at low spinning rate. Hence, this chemical system is a good case study to demonstrate the utility of the higher sample spinning rates that can be achieved by our new rotor design. We expect this new capability will be useful for exploring solid-state, including interfacial, chemistry at new levels of high-pressure in a wide variety of fields.
Miller QRS, CJ Thompson, JS Loring, CF Windisch, Jr, ME Bowden, DW Hoyt, JZ Hu, BW Arey, KM Rosso, and HT Schaef. 2013. "Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids." International Journal of Greenhouse Gas Control 15:104-118. doi:10.1016/j.ijggc.2013.02.005 Abstract Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratory research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.
Wang Z, AR Felmy, CJ Thompson, JS Loring, AG Joly, KM Rosso, HT Schaef, and DA Dixon. 2013. "Near-Infrared Spectroscopic Investigation of Water in Supercritical CO2 and the Effect of CaCl2." Fluid Phase Equilibria 338:155-163. doi:10.1016/j.fluid.2012.11.012 Abstract Near-infrared (NIR) spectroscopy was applied to investigate the dissolution and chemical interaction of water dissolved into supercritical carbon dioxide (scCO2) and the influence of CaCl2 in the co-existing aqueous phase at fo empe e : 40 50 75 nd 100 C at 90 atm. Consistent with the trend of the vapor pressure of water, the solubility of pure water in scCO2 inc e ed f om 40 ˚C (0.32 mole%) o 100 ˚C (1.61 mole%). The presence of CaCl2 negatively affects the solubility of water in scCO2: at a given temperature and pressure the solubility of water decreased as the concentration of CaCl2 in the aqueous phase increased, following the trend of the activity of water. A 40 ˚C, the water concentration in scCO2 in contact with saturated CaCl2 aqueous solution was only 0.16 mole%, a drop of more than 50% as compared to pure water while that a 100 ˚C was 1.12 mole%, a drop of over 30% as compared to pure water, under otherwise the same conditions. Analysis of the spectral profiles suggested that water dissolved into scCO2 exists in the monomeric form under the evaluated temperature and pressure conditions, for both neat water and CaCl2 solutions. However, its rotational degrees of freedom decrease at lower temperatures due to higher fluid densities, leading to formation of weak H2O:CO2 Lewis acid-base complexes. Similarly, the nearly invariant spectral profiles of dissolved water in the presence and absence of saturated CaCl2 under the same experimental conditions was taken as evidence that CaCl2 dissolution in scCO2 was limited as the dissolved Ca2+/CaCl2 would likely be highly hydrated and would alter the overall spectra of waters in the scCO2 phase.
Yang X, TD Scheibe, MC Richmond, WA Perkins, SJ Vogt, SL Codd, JD Seymour, and MI Mckinley. 2013. "Direct Numerical Simulation of Pore-Scale Flow in a Bead Pack: Comparison with Magnetic Resonance Imaging Observations." Advances in Water Resources 54:288-241. doi:10.1016/j.advwatres.2013.01.009 Abstract A significant body of current research is aimed at developing methods for numerical simulation of flow and transport in porous media that explicitly resolve complex pore and solid geometries, and at utilizing such models to study the relationships between fundamental pore-scale processes and macroscopic manifestations at larger (i.e., Darcy) scales. A number of different numerical methods for pore-scale simulation have been developed, and have been extensively tested and validated for simplified geometries. However, validation of pore-scale simulations of fluid velocity for complex, three-dimensional (3D) pore geometries that are representative of natural porous media is challenging due to our limited ability to measure pore-scale velocity in such systems. Recent advances in magnetic resonance imaging (MRI) offer the opportunity to measure not only the pore geometry, but also local fluid velocities under steady-state flow conditions in 3D and with high spatial resolution. In this paper, we present a 3D velocity field measured at sub-pore resolution (tens of micrometers) over a centimeter-scale 3D domain using MRI methods. We have utilized the measured pore geometry to perform 3D simulations of Navier-Stokes flow over the same domain using direct numerical simulation techniques. We present a comparison of the numerical simulation results with the measured velocity field. It is shown that the numerical results match the observed velocity patterns well overall except for a variance and small systematic scaling which can be attributed to the known experimental error in the MRI measurements. The comparisons presented here provide strong validation of the pore-scale simulation methods and new insights for interpretation of uncertainty in MRI measurements of pore-scale velocity. This study also provides a potential benchmark for future comparison of other pore-scale simulation methods.
McCloy JS, BJ Riley, AS Lipton, CF Windisch, Jr, NM Washton, MJ Olszta, and CP Rodriguez. 2013. "Structure and Chemistry in Halide Lead-Tellurite Glasses." Journal of Materials Chemistry 117(7):3456-3466. doi:10.1021/jp310820t Abstract A series of TeO2-PbO glasses were fabricated with increasing fractions of mixed alkali, alkaline earth, and lanthanide chlorides. The glass and crystal structure was studied with Raman spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction, and electron microscopy. As the chloride fraction increased, the medium-range order in the glass decreased up to a critical point (~14 mass% of mixed chlorides), above which the glasses became phase-separated. Resulting phases are a TeO2/PbO-rich phase and a crystalline phase rich in alkali chlorides. The 125Te NMR indicates, contrary to previous studies, that Te site distribution did not change with increased concentrations of M+, M2+, and M3+ cations, but rather is controlled by the Te/Pb molar ratio. The 207Pb NMR shows that two Pb species exist and their relative concentration changes nearly linearly with addition of the mixed chlorides, indicating that the additives to the TeO2-PbO glass are accommodated by changing the Pb species. The 23Na and 35Cl NMR indicate that Na and Cl are distributed in the single-phase glass phase up to the critical point, and at higher concentrations partition to crystalline phases. Transmission electron microscopy shows that the sample at the critical point contains ~10 nm seed nuclei that increase in size and concentration with exposure to the electron beam.
Fanizza MF, H Yoon, C Zhang, M Oostrom, TW Wietsma, NJ Hess, ME Bowden, TJ Strathmann, KT Finneran, and CJ Werth. 2013. "Pore-Scale Evaluation of Uranyl Phosphate Precipitation in a Model Groundwater System." Water Resources Research 49(2):874-890. doi:10.1002/wrcr.20088 Abstract The abiotic precipitation of uranium (U(VI)) was evaluated in a microfluidic pore network (i.e. micromodel) to assess the efficacy of using a phosphate amendment to immobilize uranium in groundwater. U(VI) was mixed transverse to the direction of flow with hydrogen phosphate (HPO42-), in the presence or absence of calcium (Ca2+) or sulfate (SO42-), in order to identify precipitation rates, morphology and types of minerals formed, and effects of mineral precipitates on pore blockage. Precipitation occurred over the time scale of hours to days. Relative to when only U(VI) and HPO42- were present, precipitation rates were 2.3X slower when SO42- was present, and 1.4X faster when Ca2+ was present; larger crystals formed in the presence of SO42-. Raman backscattering spectroscopy and micro X-ray diffraction (μ-XRD) results both showed that the only mineral precipitated was chernikovite, UO2HPO4•4H2O; energy dispersive x-ray spectroscopy results indicate that Ca and S are not incorporated into the chernikovite lattice. A pore scale model was developed, and simulation results of saturation ratio (SR=Q/Ksp) suggest that chernikovite is the least thermodynamically favored mineral to precipitate (0<SR<1) compared to uranyl hydrogen phosphate and Na-Autunite (13<SR<40), and uranyl orthophosphate and Ca-autunite (when Ca2+ is present) (SR>105). Fluorescent tracer studies and laser confocal microscopy images showed that densely aggregated precipitates blocked pores and reduced permeability. The results suggest that uranium precipitation with phosphate as chernikovite is rapid on the time scale of remediation for the conditions considered, and can block pores, alter fluid flow paths, and potentially limit mixing and precipitation.
Liu Y, C Zhang, D Hu, MS Kuhlenschmidt, TB Kuhlenschmidt, SE Mylon, R Kong, R Bhargava, and TH Nguyen. 2013. "Role of collector alternating charged patches on transport of Cryptosporidium parvum oocyst in a patchwise charged heterogeneous micromodel." Environmental Science & Technology 47(6):2670-2678. doi:10.1021/es304075j Abstract The role of collector surface charge heterogeneity on transport of Cryptosporidium parvum oocyst and carboxylate microsphere in 2-dimensional micromodels was studied. The cylindrical silica collectors within the micromodels were coated with 0, 10, 20, 50 and 100% Fe2O3 patches. The experimental values of average single collector removal efficiencies (η) of the Fe2O3 patches and on the entire collectors were determined. In the presence of significant (>3500 kT) Derjaguin–Landau–Verwey–Overbeek (DLVO) energy barrier between the microspheres and the silica collectors at pH 5.8 and 8.1, the values of η determined for Fe2O3 patches were significantly less (p < 0.05, t-test) than that obtained for collectors coated entirely with Fe2O3. However, η on Fe2O3 patches for microspheres at pH 4.4 and for oocysts at pH 5.8 and 8.1, where the DLVO energy barrier was relatively small (ca. 200-360 kT), were significantly greater (p < 0.05, t-test) than that on the collectors coated entirely with Fe2O3. The dependence of η determined for Fe2O3 patches on the DLVO energy barrier indicated the importance of periodic favorable and unfavorable electrostatic interactions between colloids and collectors with alternating Fe2O3 and silica patches. Differences between experimentally determined η and that predicted by a patchwise geochemical heterogeneous model was observed, but can be explained by the model’s lack of consideration for the spatial distribution of charge heterogeneity on the collector surface and colloid migration on patchwise heterogeneous collectors.

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