Sarah J. Vogt

Permeability of a growing biofilm in a porous media fluid flow analyzed by magnetic resonance displacement-relaxation correlations

Biofilm growth in porous media is difficult to study non‐invasively due to the opaqueness and heterogeneity of the systems. Magnetic resonance is utilized to non‐invasively study water dynamics within porous media. Displacement‐relaxation correlation experiments were performed on fluid flow during biofilm growth in a model porous media of mono‐dispersed polystyrene beads. The spin–spin T2 magnetic relaxation distinguishes between the biofilm phase and bulk fluid phase due to water–biopolymer interactions present in the biofilm, and the flow dynamics are measured using PGSE NMR experiments. By correlating these two measurements, the effects of biofilm growth on the fluid dynamics can be separated into a detailed analysis of both the biofilm phase and the fluid phase simultaneously within the same experiment. Within the displacement resolution of these experiments, no convective flow was measured through the biomass. An increased amount of longitudinal hydrodynamic dispersion indicates increased hydrodynamic mixing due to fluid channeling caused by biofilm growth. The effect of different biofilm growth conditions was measured by varying the strength of the bacterial growth medium. Biotechnol. Bioeng. 2013; 110: 1366–1375.

Simultaneous Gaussian and exponential inversion for improved analysis of shales by NMR relaxometry

Nuclear magnetic resonance (NMR) relaxometry is commonly used to provide lithology-independent porosity and pore-size estimates for petroleum resource evaluation based on fluid-phase signals. However in shales, substantial hydrogen content is associated with solid and fluid signals and both may be detected. Depending on the motional regime, the signal from the solids may be best described using either exponential or Gaussian decay functions. When the inverse Laplace transform, the standard method for analysis of NMR relaxometry results, is applied to data containing Gaussian decays, this can lead to physically unrealistic responses such as signal or porosity overcall and relaxation times that are too short to be determined using the applied instrument settings. We apply a new simultaneous Gaussian-Exponential (SGE) inversion method to simulated data and measured results obtained on a variety of oil shale samples. The SGE inversion produces more physically realistic results than the inverse Laplace transform and displays more consistent relaxation behavior at high magnetic field strengths. Residuals for the SGE inversion are consistently lower than for the inverse Laplace method and signal overcall at short T2 times is mitigated. Beyond geological samples, the method can also be applied in other fields where the sample relaxation consists of both Gaussian and exponential decays, for example in material, medical and food sciences.

Magnetic resonance diffusion and relaxation characterization of water in the unfrozen vein network in polycrystalline ice and its response to microbial metabolic products

Polycrystalline ice, as found in glaciers and the ice sheets of Antarctica, is a low porosity porous media consisting of a complicated and dynamic pore structure of liquid-filled intercrystalline veins within a solid ice matrix. In this work, Nuclear Magnetic Resonance measurements of relaxation rates and molecular diffusion, useful for probing pore structure and transport dynamics in porous systems, were used to physically characterize the unfrozen vein network structure in ice and its response to the presence of metabolic products produced by V3519-10, a cold tolerant microorganism isolated from the Vostok ice core. Recent research has found microorganisms that can remain viable and even metabolically active within icy environments at sub-zero temperatures. One potential mechanism of survival for V3519-10 is secretion of an extracellular ice binding protein that binds to the prism face of ice crystals and inhibits ice recrystallization, a coarsening process resulting in crystal growth with ice aging. Understanding the impact of ice binding activity on the bulk vein network structure in ice is important to modeling of frozen geophysical systems and in development of ice interacting proteins for biotechnology applications, such as cryopreservation of cell lines, and manufacturing processes in food sciences. Here, we present the first observations of recrystallization inhibition in low porosity ice containing V3519-10 extracellular protein extract as measured with Nuclear Magnetic Resonance and Magnetic Resonance Imaging.

Microbial and algal alginate gelation characterized by magnetic resonance

Advanced magnetic resonance (MR) relaxation and diffusion correlation measurements and imaging provide a means to non-invasively monitor gelation for biotechnology applications. In this study, MR is used to characterize physical gelation of three alginates with distinct chemical structures; an algal alginate, which is not O-acetylated but contains poly guluronate (G) blocks, bacterial alginate from Pseudomonas aeruginosa, which does not have poly-G blocks, but is O-acetylated at the C2 and/or C3 of the mannuronate residues, and alginate from a P. aeruginosa mutant that lacks O-acetyl groups. The MR data indicate that diffusion-reaction front gelation with Ca(2+) ions generates gels of different bulk homogeneities dependent on the alginate structure. Shorter spin-spin T(2) magnetic relaxation times in the alginate gels that lack O-acetyl groups indicate stronger molecular interaction between the water and biopolymer. The data characterize gel differences over a hierarchy of scales from molecular to system size.

Biofilm detection in natural unconsolidated porous media using a low-field magnetic resonance system.

The extent to which T(2) relaxation measurements can be used to determine biofouling in several natural geological sand media using a low-field (275 kHz, 6.5 mT) NMR system has been demonstrated. It has been previously shown that, at high laboratory strength fields (300 MHz, 7 T), T(2) techniques can be used as a bioassay to confirm the growth of biofilm inside opaque porous media with low magnetic susceptibilities such as borosilicate or soda lime glass beads. Additionally decreases in T(2) can be associated with intact biofilm as opposed to degraded biofilm material. However, in natural geological media, the strong susceptibility gradients generated at high fields dominated the T(2) relaxation time distributions and biofilm growth could not be reliably detected. Samples studied included Bacillus mojavensis biofilm in several sand types, as well as alginate solution and alginate gel in several sand types. One of the sand types was highly magnetic. Data was collected with a low-field (275 kHz, 6.5 mT) benchtop NMR system using a CPMG sequence with an echo time of 1.25 ms providing the ability to detect signals with T(2) greater than 1 ms. Data presented here clearly demonstrate that biofilm can be reliably detected and monitored in highly magnetically susceptible geological samples using a low-field NMR spectrometer indicating that low-field NMR could be viable as a biofilm sensor at bioremedation sites.

Detection of biological uranium reduction using magnetic resonance.

The conversion of soluble uranyl ions (UO  22+ ) by bacterial reduction to sparingly soluble uraninite (UO2(s)) is being studied as a way of immobilizing subsurface uranium contamination. Under anaerobic conditions, several known types of bacteria including iron and sulfate reducing bacteria have been shown to reduce U (VI) to U (IV). Experiments using a suspension of uraninite (UO2(s)) particles produced by Shewanella putrefaciens CN32 bacteria show a dependence of both longitudinal (T1) and transverse (T2) magnetic resonance (MR) relaxation times on the oxidation state and solubility of the uranium. Gradient echo and spin echo MR images were compared to quantify the effect caused by the magnetic field fluctuations (

Interfacial tension measurements using MRI drop shape analysis.

T_{2}^{*}

Capillary trapping quantification in sandstones using NMR relaxometry

) of the uraninite particles and soluble uranyl ions. Since the precipitate studied was suspended in liquid water, the effects of concentration and particle aggregation were explored. A suspension of uraninite particles was injected into a polysaccharide gel, which simulates the precipitation environment of uraninite in the extracellular biofilm matrix. A reduction in the T2 of the gel surrounding the particles was observed. Tests done in situ using three bioreactors under different mixing conditions, continuously stirred, intermittently stirred, and not stirred, showed a quantifiable T2 magnetic relaxation effect over the extent of the reaction. Biotechnol. Bioeng. 2012; 109:877–883.

NMR Measurements of Tortuosity in Partially Saturated Porous Media

Accurate interfacial tension data for fluid systems such as hydrocarbons and water is essential to many applications such as reservoir oil and gas recovery predictions. Conventional interfacial tension measurement techniques typically use optical images to analyze droplet shapes but require that the continuous-phase fluid be optically transparent and that the fluids are not refractive index matched. Magnetic resonance images obtain contrast between fluids using other mechanisms such as magnetic relaxation weighting, so systems that are impossible to measure with optical methods may be analyzed. In this article, we present high-field (9.4 T) MRI images of various droplets analyzed with axisymmetric drop shape analysis. The resultant interfacial tension data show good agreement with literature data. The method is subsequently demonstrated using both opaque continuous phases and refractive-index-matched fluids. We conclude with a brief consideration of the potential to extrapolate the methodology to lower magnetic fields (0.3 T), featuring more accessible hardware; although droplet imaging is possible, resolution and stability do not currently permit accurate interfacial tension measurements.

Direct numerical simulation of pore-scale flow in a bead pack: Comparison with magnetic resonance imaging observations

Capillary trapping of a non-wetting phase arising from two-phase immiscible flow in sedimentary rocks is critical to many geoscience scenarios, including oil and gas recovery, aquifer recharge and, with increasing interest, carbon sequestration. Here we demonstrate the successful use of low field 1H Nuclear Magnetic Resonance (NMR) to quantify capillary trapping; specifically we use transverse relaxation time (T2) time measurements to measure both residual water (wetting phase) content and the surface-to-volume ratio distribution (which is proportional to pore size) of the void space occupied by this residual water. Critically we systematically confirm this relationship between T2 and pore size by quantifying inter-pore magnetic field gradients due to magnetic susceptibility contrast, and demonstrate that our measurements at all water saturations are unaffected. Diffusion in such field gradients can potentially severely distort the T2-pore size relationship, rendering it unusable. Measurements are performed for nitrogen injection into a range of water-saturated sandstone plugs at reservoir conditions. Consistent with a water-wet system, water was preferentially displaced from larger pores while relatively little change was observed in the water occupying smaller pore spaces. The impact of cyclic wetting/non-wetting fluid injection was explored and indicated that such a regime increased non-wetting trapping efficiency by the sequential occupation of the most available larger pores by nitrogen. Finally the replacement of nitrogen by CO2 was considered; this revealed that dissolution of paramagnetic minerals from the sandstone caused by its exposure to carbonic acid reduced the in situ bulk fluid T2 relaxation time on a timescale comparable to our core flooding experiments. The implications of this for the T2-pore size relationship are discussed.