Magic Angle Spinning Effects on Longitudinal NMR Relaxation: 15N in L-Histidine

Solid-state magnetic resonance is a unique technique that can reveal the dynamics of complex biological systems with atomic resolution. Longitudinal relaxation is a mechanism that returns longitudinal nuclear magnetization to its thermal equilibrium by incoherent processes. The measured longitudinal relaxation rate constant however represents the combination of both incoherent and coherent contributions to the change of nuclear magnetization. This work demonstrates the effect of magic angle spinning rate on the longitudinal relaxation rate constant in two model compounds: L-histidine hydrochloride monohydrate and glycine serving as proxies for isotopically-enriched biological materials. Most notably, it is demonstrated that the longitudinal 15N relaxation of the two nitrogen nuclei in the imidazole ring in histidine is reduced by almost three orders of magnitude at the condition of rotational resonance with the amine, while the amine relaxation rate constant is increased at these conditions. The observed phenomenon may have radical implications for the solid-state magnetic resonance in biophysics and materials, especially in the proper measurement of dynamics and as a selective serial transfer step in dynamic nuclear polarization

Exponential Capillary Pressure Functions in Sedimentary Rocks

The Brooks-Corey power-law capillary pressure model is commonly imposed on core analysis data without verifying the validity of its underlying assumptions. The Brooks-Corey model, originally developed to model the pressure head during the drainage of soil, is only valid at low wetting phase saturations. However, such models are often applied in petroleum production simulations and may lead to erroneous recovery factors when the saturation range of interest is far from the end points. We demonstrate that exponential models work much better for capillary pressure compared to the Brooks-Corey model over a wide saturation range. Mercury injection porosimetry, petrographic image analysis, and magnetic resonance studies suggest that the pore and throat size distribution in many rocks are log-normally distributed. This fact was previously employed to calculate the capillary pressure function as a function of saturation for pore size distributions described by atruncated log-normal distribution. Employing a Taylor series expansion, we simplify the random fractal capillary pressure model of Hunt to Pc = exp(a − bS), where S is the wetting phase saturation, and a and b characteristic of the porous medium. An extensive dataset of seventeen centrifuge capillary pressure measurements were used in this research to demonstrate the merit of the new method. For both sandstones and carbonates, the logarithm of capillary pressure showed a linear relationship with saturation as observed by magnetic resonance imaging centrifuge capillary pressure measurements over a wide saturation range. This work demonstrates that: (a) in semi-log plots of capillary pressure as a function of saturation, capillary pressurewill vary linearly over a wide saturation range, (b) such a plot as described in (a) will show the uni-or bimodal pore size distribution of the rock, (c) the exponential capillary pressure function simplifies analytical modelsthat use the capillary pressure function, for example oil recovery models for fractured reservoirs

Monitoring gas hydrate formation with magnetic resonance imaging in a metallic core holder

Methane hydrate deposits world-wide are promising sources of natural gas. Magnetic Resonance Imaging (MRI) has proven useful in previous studies of hydrate formation. In the present work, methane hydrate formation in a water saturated sand pack was investigated employing an MRI-compatible metallic core holder at low magnetic field with a suite of advanced MRI methods developed at the UNB MRI Centre. The new MRI methods are intended to permit observation and quantification of residual fluids in the pore space as hydrate forms. Hydrate formation occurred in the water-saturated sand at 1500 psi and 4 °C. The core holder has a maximum working pressure of 4000 psi between -28 and 80 °C. The heat-exchange jacket enclosing the core holder enabled very precise control of the sample temperature. A pure phase encode MRI technique, SPRITE, and a bulk T1-T2 MR method provided high quality measurements of pore fluid saturation. Rapid 1D SPRITE MRI measurements time resolved the disappearance of pore water and hence the growth of hydrate in the sand pack. 3D π-EPI images confirmed that the residual water was inhomogeneously distributed along the sand pack. Bulk T1-T2 measurements discriminated residual water from the pore gas during the hydrate formation. A recently published local T1-T2 method helped discriminate bulk gas from the residual fluids in the sample. Hydrate formation commenced within two hours of gas supply. Hydrate formed throughout the sand pack, but maximum hydrate was observed at the interface between the gas pressure head and the sand pack. This irregular pattern of hydrate formation became more uniform over 24 hours. The rate of hydrate formation was greatest in the first two hours of reaction. An SE-SPI T2 map showed the T2 distribution changed considerably in space and time as hydrate formation continued. Changes in the T2 distribution are interpreted as pore level changes in residual water content and environment

Magnetic resonance free induction decay in geological porous materials

Magnetic resonance is an important noninvasive technology across life sciences and industry. Free induction decay is the simplest $$^{\mathrm {1}}$$H magnetic resonance measurement method and an important means of probing fast-decaying signals in porous materials such as rocks, lung, and bone. It is commonly assumed that the free induction decay in geological porous materials is single-exponential. We experimentally observed two regimes of free induction decay behavior in geological porous materials: single-exponential and non-exponential decay. Numerical simulations that match experimental data highlight the effect of mass diffusion, especially in the single-exponential behavior. These two regimes of free induction decay in porous materials are associated with a bifurcation point in the solutions of the Bloch–Torrey equation for diffusion of fluids in confined domains in the presence of internal magnetic field gradients. This finding facilitates the extraction of absolute internal magnetic field gradient intensities from simple free induction decay measurements in the laboratory and field. This work also warns against common single-exponential assumptions in surface magnetic resonance methods employed in surveying underground water aquifers

Exponential Capillary Pressure Functions in Sedimentary Rocks

The Brooks-Corey power-law capillary pressure model is commonly imposed on core analysis data without verifying the validity of its underlying assumptions. The Brooks-Corey model, originally developed to model the pressure head during the drainage of soil, is only valid at low wetting phase saturations. However, such models are often applied in petroleum production simulations and may lead to erroneous recovery factors when the saturation range of interest is far from the end points. We demonstrate that exponential models work much better for capillary pressure compared to the Brooks-Corey model over a wide saturation range. Mercury injection porosimetry, petrographic image analysis, and magnetic resonance studies suggest that the pore and throat size distribution in many rocks are log-normally distributed. This fact was previously employed to calculate the capillary pressure function as a function of saturation for pore size distributions described by atruncated log-normal distribution. Employing a Taylor series expansion, we simplify the random fractal capillary pressure model of Hunt to Pc = exp(a − bS), where S is the wetting phase saturation, and a and b characteristic of the porous medium. An extensive dataset of seventeen centrifuge capillary pressure measurements were used in this research to demonstrate the merit of the new method. For both sandstones and carbonates, the logarithm of capillary pressure showed a linear relationship with saturation as observed by magnetic resonance imaging centrifuge capillary pressure measurements over a wide saturation range. This work demonstrates that: (a) in semi-log plots of capillary pressure as a function of saturation, capillary pressurewill vary linearly over a wide saturation range, (b) such a plot as described in (a) will show the uni-or bimodal pore size distribution of the rock, (c) the exponential capillary pressure function simplifies analytical modelsthat use the capillary pressure function, for example oil recovery models for fractured reservoirs