Magnetic Resonance Relaxation Times Research Articles

Determining adsorbate configuration on alumina surfaces with (13)C nuclear magnetic resonance relaxation time analysis.

Relative strengths of surface interaction for individual carbon atoms in acyclic and cyclic hydrocarbons adsorbed on alumina surfaces are determined using chemically resolved (13)C nuclear magnetic resonance (NMR) T1 relaxation times. The ratio of relaxation times for the adsorbed atoms T1,ads to the bulk liquid relaxation time T1,bulk provides an indication of the mobility of the atom. Hence a low T1,ads/T1,bulk ratio indicates a stronger surface interaction. The carbon atoms associated with unsaturated bonds in the molecules are seen to exhibit a larger reduction in T1 on adsorption relative to the aliphatic carbons, consistent with adsorption occurring through the carbon-carbon multiple bonds. The relaxation data are interpreted in terms of proximity of individual carbon atoms to the alumina surface and adsorption conformations are inferred. Furthermore, variations of interaction strength and molecular configuration have been explored as a function of adsorbate coverage, temperature, surface pre-treatment, and in the presence of co-adsorbates. This relaxation time analysis is appropriate for studying the behaviour of hydrocarbons adsorbed on a wide range of catalyst support and supported-metal catalyst surfaces, and offers the potential to explore such systems under realistic operating conditions when multiple chemical components are present at the surface.

Combining Neutron and Magnetic Resonance Imaging to Study the Interaction of Plant Roots and Soil

The soil in direct vicinity of the roots, the root-soil interface or so called rhizosphere, is heavily modified by the activity of roots, compared to bulk soil, e.g. in respect to microbiology and soil chemistry. It has turned out that the root-soil interface, though small in size, also plays a decisive role in the hydraulics controlling the water flow from bulk soil into the roots. A promising approach for the non-invasive investigation of water dynamics, water flow and solute transport is the combination of the two imaging techniques magnetic resonance imaging (MRI) and neutron imaging (NI). Both methods are complementary, because NI maps the total proton density, possibly amplified by NI tracers, which usually corresponds to total water content, and is able to detect changes and spatial patterns with high resolution. On the other side, nuclear magnetic resonance relaxation times reflect the interaction between fluid and matrix, while also a mapping of proton spin density and thus water content is possible. Therefore MRI is able to classify different water pools via their relaxation times additionally to the water distribution inside soil as a porous medium. We have started such combined measurements with the approach to use the same samples and perform tomography with each imaging method at different location and short-term sample transfer.

Pore size analysis from low field NMR spin–spin relaxation measurements of porous microspheres

The porous structure characteristics of twenty-one porous microspheres with agarose framework were investigated based on the low-field nuclear magnetic resonance (LF NMR) relaxation time (T 2) distribution measurements. The feasibility of the technique was confirmed by direct relationship between T 2 and the mean pore size of the polymer networks (Rh) of agarose hydrogel which was established using the “Fiber-Cell” model. The expected pore radius distribution curve was obtained and the reliability was validated by comparing them with the results obtained by inverse size-exclusion chromatography. Thereafter, the technique was applied to characterize the pore size distribution (PSD) of soft microspheres and the pore size transformation of microspheres with or without grafted polymers in the process of protein adsorption. All of these results strongly support LF NMR as a promising, rapid and nondestructive technique for the determination of PSDs in many kinds of soft porous microspheres.

Physical Activity and Spatial Differences in Medial Knee T1rho and T2 Relaxation Times in Knee Osteoarthritis

Cross-sectional. To investigate the association between knee loading- related osteoarthritis (OA) risk factors (obesity, malalignment, and physical activity) and medial knee laminar (superficial and deep) T1rho and T2 relaxation times. The interaction of various modifiable loading-related knee risk factors and cartilage health in knee OA is currently not well known. Participants with and without knee OA (n = 151) underwent magnetic resonance imaging at 3 T for superficial and deep cartilage T1rho and T2 magnetic resonance relaxation times in the medial femur (MF) and medial tibia (MT). Other variables included radiographic Kellgren-Lawrence (KL) grade, alignment, pain and symptoms using the Knee injury and Osteoarthritis Outcome Score, and physical activity using the International Physical Activity Questionnaire (IPAQ). Individuals with a KL grade of 4 were excluded. Group differences were calculated using 1-way analysis of variance, adjusting for age and body mass index. Linear regression models were created with age, sex, body mass index, alignment, KL grade, and the IPAQ scores to predict the laminar T1rho and T2 times. Total IPAQ scores were the only significant predictors among the loading-related variables for superficial MF T1rho (P = .005), deep MT T1rho (P = .026), and superficial MF T2 (P = .049). Additionally, the KL grade predicted the superficial MF T1rho (P = .023) and deep MT T1rho (P = .022). Higher physical activity levels and worse radiographic severity of knee OA, but not obesity or alignment, were associated with worse cartilage composition.

Interpretation of NMR relaxation as a tool for characterising the adsorption strength of liquids inside porous materials.

Nuclear magnetic resonance (NMR) relaxation times are shown to provide a unique probe of adsorbate–adsorbent interactions in liquid-saturated porous materials. A short theoretical analysis is presented, which shows that the ratio of the longitudinal to transverse relaxation times (T1/T2) is related to an adsorbate–adsorbent interaction energy, and we introduce a quantitative metric esurf (based on the relaxation time ratio) characterising the strength of this surface interaction. We then consider the interaction of water with a range of oxide surfaces (TiO2 anatase, TiO2 rutile, γ-Al2O3, SiO2, θ-Al2O3 and ZrO2) and show that esurf correlates with the strongest adsorption sites present, as determined by temperature programmed desorption (TPD). Thus we demonstrate that NMR relaxation measurements have a direct physical interpretation in terms of the characterisation of activation energy of desorption from the surface. Further, for a series of chemically similar solid materials, in this case a range of oxide materials, for which at least two calibration values are obtainable by TPD, the esurf parameter yields a direct estimate of the maximum activation energy of desorption from the surface. The results suggest that T1/T2 measurements may become a useful addition to the methods available to characterise liquid-phase adsorption in porous materials. The particular motivation for this work is to characterise adsorbate–surface interactions in liquid-phase catalysis.

Age related reduction of T1rho and T2 magnetic resonance relaxation times of lumbar intervertebral disc.

This report aims to study the age related T1rho and T2 relaxation time changes in lumbar intervertebral disc. Lumbar sagittal magnetic resonance imaging (MRI) was performed with a 3 Tesla scanner in 52 subjects. With a spin-lock frequency of 500 Hz, T1rho was measured using a rotary echo spin-lock pulse embedded in a 3D balanced fast field echo sequence. A multi-echo turbo spin echo sequence was used for T2 mapping. Regions-of-interest were drawn over the T1rho and T2 maps, including nucleus pulposus and annulus fibrosus. For L1/2-L4/5 discs, results showed the age associated reduction of T1rho of nucleus pulposus had a of slope of -1.06, the reduction of T2 of nucleus pulposus had a slope of -1.47, the reduction of T1rho of annulus fibrosus had a slope of -0.25, and the reduction of T2 of annulus fibrosus had a slope of -0.18, with all the slopes significantly non-zero. In nucleus pulposus the slope of T2 was slightly steeper than that of T1rho (P=0.085), while in annulus fibrosus the slope of T1rho was slightly steeper than that of T2 (P=0.31). We conclude that significant age related reduction of T1rho and T2 magnetic resonance relaxation times of lumbar intervertebral disc was observed, however, the relative performances of T1rho vs. T2 were broadly similar.

Dynamics of methanol in ionic liquids: validity of the Stokes-Einstein and Stokes-Einstein-Debye relations.

The validity of Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations for methanol in the physical environment of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is studied by means of nuclear magnetic resonance (NMR) relaxation time experiments, viscosity measurements and molecular dynamics (MD) simulations. The reorientational correlation times of the hydroxyl groups of pure methanol and of methanol in the IL/methanol mixtures were determined. For that purpose an approach for estimating NMR deuteron quadrupole coupling constants, presented by Wendt and Farrar (Mol. Phys. 1998, 95, 1077-1081), was confirmed. The self-diffusion coefficients of methanol were taken from the MD simulations. The viscosities of all systems were then measured and the SE and SED relations validated. For pure methanol both relations are valid, whereas they become increasingly invalid with increasing IL concentration, as indicated by effective volumes and radii that are too low. The deviation from the SE and SED relations could be related to dynamical heterogeneities described by the non-Gaussian parameter α(t) obtained from MD simulations. For pure methanol, α(t) is close to zero in accord with the validity of both relations. With increasing IL concentration the dynamical heterogeneities of methanol increase strongly. The times t* at the maximum of α(t) increase linearly with the relative number of methanol monomers in the mixtures. Thus, the dynamical heterogeneities are largest for single methanol molecules fully embedded in the IL environment. In their own environment methanol molecules are highly mobile, whereas in the IL-rich region the mobility is strongly reduced leading to the non-validity of SE and SED relations.

Using magnetic resonance imaging to study enzymatic hydrogelation.

Herein, we report, for the first time, the use of MRI methods to study enzymatic hydrogelation. Supramolecular hydrogels have been exploited as biomaterials for many applications. However, behaviors of the water molecules encapsulated in hydrogels have not been fully understood. In this work, we designed a precursor 1 which could self-assemble into nanofibers and form hydrogel I (gel I) upon the catalysis of phosphatase. The differences of mechanic property, pore size, water diffusion rate, and magnetic resonance relaxation times T1 and T2 of gel I containing different concentrations of 1 were systematically studied and analyzed. T1, T2, and diffusion-weighted (1)H MR images from gel I phantoms were obtained at 9.4 T. Analyses of the MRI data uncovered how the density of the nanofiber networks affects the relaxation behaviors of the water protons encapsulated in such hydrogels. Rheological analyses and cryo-TEM observations showed increased gel elasticities with increased concentrations of 1 while the pore sizes of gel I decreased. This also resulted in an increase in the proton relaxation rate (i.e., shortened T1, T2, and apparent diffusion coefficient (ADC)) for the water encapsulated in the hydrogel. With MRI, our study provides a new in vitro method to potentially mimic and study in vivo diseases that involve fibrous aggregates.

Nuclear magnetic resonance characterization of shallow marine sediments from the Nankai Trough, Integrated Ocean Drilling Program Expedition 333

AbstractWe measured nuclear magnetic resonance (NMR) relaxation times on samples from Integrated Ocean Drilling Program Expedition 333 Sites C0011, C0012, and C0018. We compared our results to permeability, grain size, and specific surface measurements, pore size distributions from mercury injection capillary pressure, and mineralogy from X‐ray fluorescence. We found that permeability could be predicted from NMR measurements by including grain size and specific surface to quantify pore networks and that grain size is the most important factor in relating NMR response to permeability. Samples within zones of anomalously high porosity from Sites C0011 and C0012 were found to have different NMR‐permeability relationships than samples from outside these zones, suggesting that the porosity anomaly is related to a fundamental difference in pore structure. We additionally estimated the size of paramagnetic sites that cause proton relaxation and found that in most of our samples, paramagnetic material is present mainly as discrete, clay‐sized grains. This distribution of paramagnetic material may cause pronounced heterogeneity in NMR properties at the pore scale that is not accounted for in most NMR interpretation techniques. Our results provide important insight into the microstructure of marine sediments in the Nankai Trough.

Molecular Dynamics of Proteins Investigated by NMR Relaxation Methods

The nuclear magnetic resonance relaxation times of solvent water nuclei are known to decrease upon addition of diamagnetic solute protein. For this reason NMR relaxation methods are able to provide information on molecular dynamics changes of water protons and their interaction with macromolecules' surfaces. We present results of measurements of relaxation rates R1 = 1/T1, R2 = 1/T2 and R1ρ = 1/T1ρ in the rotating frame for three proteins: chicken egg white lysozyme, egg white albumin, and bovine serum albumin, obtained at proton resonant frequency of 60 MHz. Besides the relaxation rates dependences on concentration in the 4 23% (g/100 g solution) range, the analysis of the Carr Purcell Meiboom Gill CPMG multi-echo T2 experiments with variable pulse rate τ was performed. The dependences of relaxation rates on protein concentration are linear at low concentration. When protein concentration increases the slope of the straight line rapidly changes at so-called critical concentration which depends on MW of the diluted protein. Investigated dispersion of T2, obtained using the CPMG method with a variable pulse rate, for concentrations higher and lower than the critical one, exhibits unequal behavior. At high concentration one-exponential curves and at low concentration two-exponential curves correspond closely with experimental data. The obtained parameters of exponents allow an estimation of the ratio of the amount of water with the determined motion freedom, that is free and bounded water, in solution. We showed that the CPMG dispersion method applied to aqueous protein solutions may widen the current understanding of the nature of molecular dynamics of hydrated water protons in non-perturbed environment.

Iron and noncontrast magnetic resonance T2* as a marker of intraplaque iron in human atherosclerosis

Iron has been implicated in atherogenesis and plaque destabilization, whereas less is known about iron-related proteins in this disease. We compared ex vivo quantities with in vivo vessel wall T2*, which is a noncontrast magnetic resonance relaxation time that quantitatively shortens with increased tissue iron content. We also tested the hypothesis that patients with carotid atherosclerosis have abnormal T2* times vs controls that would help support a role for iron in human atherosclerosis. Forty-six patients undergoing carotid endarterectomy and 14 subjects without carotid disease were prospectively enrolled to undergo carotid magnetic resonance imaging. Ex vivo measurements were performed on explanted plaque and 17 mammary artery samples. Plaques vs normal arteries had higher levels of ferritin (median, 7.3 [interquartile range (IQR), 4-13.8] vs 1.0 [IQR, 0.6-1.3] ng/mg; P < .001) and oxidized low-density lipoprotein (median, 0.17 [IQR, 0.12-0.30] vs 0.01 [IQR, 0.003-0.03] ng/mg; P < .001) as well as hepcidin (median, 8.7 [IQR, 4.6-12.4] vs 2.6 [IQR, 1.3-7.0] ng/mL; P = .03); serum hepcidin levels did not distinguish atherosclerosis patients from controls (median, 40.6 [IQR, 18.8-88.6] vs 33.9 [IQR, 17.6-55.2]; P = .42). Shorter in vivo T2* paralleled larger plaque volume (ρ = -.44; P = .01), and diseased arteries had shorter T2* values compared with controls (median, 17.7 ± 4.3 vs 23.0 ± 2.4 ms; P < .001). Diseased arteries have greater levels of iron-related proteins ex vivo and shorter T2* times in vivo. Further studies should help define the role of T2* as a biomarker of iron and atherosclerosis.

A compact high-performance low-field NMR apparatus for measurements on fluids at very high pressures and temperatures

We discuss an innovative new high-performance apparatus for performing low-field Nuclear Magnetic Resonance (NMR) relaxation times and diffusion measurements on fluids at very high pressures and high temperatures. The apparatus sensor design and electronics specifications allow for dual deployment either in a fluid sampling well logging tool or in a laboratory. The sensor and electronics were designed to function in both environments. This paper discusses the use of the apparatus in a laboratory environment. The operating temperature and pressure limits, and the signal-to-noise ratio (SNR) of the new system exceed by a very wide margin what is currently possible. This major breakthrough was made possible by a revolutionary new sensor design that breaks many of the rules of conventional high pressure NMR sensor design. A metallic sample holder capable of operating at high pressures and temperatures is provided to contain the fluid under study. The sample holder has been successfully tested for operation up to 36 Kpsi. A solenoid coil wound on a slotted titanium frame sits inside the metallic sample holder and serves as an antenna to transmit RF pulses and receive NMR signals. The metal sample holder is sandwiched between a pair of gradient coils which provide a linear field gradient for pulsed field gradient diffusion measurements. The assembly sits in the bore of a low-gradient permanent magnet. The system can operate over a wide frequency range without the need for tuning the antenna to the Larmor frequency. The SNR measured on a water sample at room temperature is more than 15 times greater than that of the commercial low-field system in our laboratory. Thus, the new system provides for data acquisition more than 200 times faster than was previously possible. Laboratory NMR measurements of relaxations times and diffusion coefficients performed at pressures up to 25 Kpsi and at temperatures up to 175 °C with crude oils enlivened with dissolved hydrocarbon gases (referred to as "live oils") are shown. This is the first time low-field NMR measurements have been performed at such high temperatures and pressures on live crude oil samples. We discuss the details of the apparatus design, tuning, calibration, and operation. NMR data acquired at multiple temperatures and pressures on a live oil sample are discussed.

Rapid measurements of heterogeneity in sandstones using low-field nuclear magnetic resonance

Sandstone rocks can contain microscopic variations in composition that complicate interpretation of nuclear magnetic resonance (NMR) relaxation time measurements. In this work, methods for assessing the degree of sample heterogeneity are demonstrated in three sandstones. A two-dimensional T1–Δχapp correlation (where Δχapp is the apparent solid/liquid magnetic susceptibility contrast) reveals the microscopic heterogeneity in composition, whilst a spatially resolved T1 profile reveals the macroscopic structural heterogeneity. To perform these measurements efficiently, a rapid measure of longitudinal T1 relaxation time has been implemented on a low-field NMR spectrometer with a magnetic field strength B0=0.3T. The “double-shot” T1 pulse sequence is appropriate for analysis of porous materials in general. Example relaxation time distributions are presented for doped water phantoms to validate the method. The acquisition time of the double-shot T1 sequence is equivalent to the single-shot Carr–Purcell Meiboom–Gill (CPMG) sequence used routinely in petrophysics to measure transverse T2 relaxation. Rapid T1 measurements enable practical studies of core plugs at magnetic field strengths previously considered inappropriate, as T1 is independent of molecular diffusion through pore-scale (internal) magnetic field gradients.

Relating nuclear magnetic resonance relaxation time distributions to void-size distributions for unconsolidated sand packs

Nuclear magnetic resonance (NMR) is used in near-surface geophysics to understand the pore-scale properties of geologic material. The interpretation of NMR data in geologic material assumes that the NMR relaxation time distribution ([Formula: see text]-distribution) is a linear transformation of the void-size distribution (VSD). This interpretation assumes fast diffusion and can be violated for materials with high surface relaxivity and/or large pores. We compared [Formula: see text]-distributions to VSDs using grain-size distributions (GSDs) as a proxy for VSDs. Measurements were collected on water-saturated sand packs with a range of grain sizes and surface relaxivities, such that some samples were expected to violate the fast diffusion assumption. Samples were prepared from silica sand with three different average grain sizes and were coated with the iron-oxide mineral hematite to vary the surface relaxivity. We found analytically that outside the fast diffusion regime, the [Formula: see text]-distributions are broader than in the fast diffusion regime, which could lead to misinterpretation of NMR data. The experimental results showed that the [Formula: see text]-distributions were not linear transformations of the GSDs. The GSDs were a single peak independent of the hematite coating. The [Formula: see text]-distributions were broader than the measured GSDs, and the center of the distribution depended on the coating. Using an equation that does not assume fast diffusion to transform the [Formula: see text]-distributions to NMR-estimated VSDs resulted in distributions that were centered on a single radius. However, our attempts to recover the VSDs, as estimated from laser particle size analysis, were unsuccessful; the NMR-estimated VSDs were broader and yielded average pore radii that were much smaller than expected. We found that our approach was useful for determining relative VSDs from [Formula: see text]-distributions; however, future research is needed to develop a method for calibrating the NMR-estimated VSDs for unconsolidated sands.

Temperature‐induced changes of magnetic resonance relaxation times in the human brain: A postmortem study

Magnetic resonance relaxation times of most tissues are expected to depend on temperature, which can impact findings in postmortem magnetic resonance imaging or when using magnetic resonance imaging for relaxation-based thermometry. The purpose of this study was to investigate the exact temperature dependency of the relaxation times T(1), T(2), T(2) *, and the magnetization transfer ratio in different structures of the human brain. To prevent fixation and autolysis effects, this study was performed with fresh postmortem brain tissues. Following autopsy, coronal brain slices from five deceased subjects were subjected to relaxometry at 3T in a temperature range between 4°C and 37°C. Heating of the tissue was achieved by flushing the vacuum packed brain slices with water at a predefined temperature. T1 showed a linear dependency on temperature with the highest temperature coefficient in the cortex (17.4 ms/°C) and the lowest in the white matter (3.4 ms/°C). T(2) did not depend on temperature. T(2) * and magnetization transfer ratio scaled with temperature only in deep gray matter. The temperature coefficient for T(1) is higher than expected from previous reports and varies across brain structures. The coefficients obtained in this study can serve as reference for thermometry or for correcting quantitative postmortem magnetic resonance imaging.

Regional variations in MR relaxation of hip joint cartilage in subjects with and without femoralacetabular impingement

The objective of this study was to analyze regional variations of magnetic resonance (MR) relaxation times (T1ρ and T2) in hip joint cartilage of healthy volunteers and subjects with femoral acetabular impingement (FAI). Morphological and quantitative images of the hip joints of 12 healthy volunteers and 9 FAI patients were obtained using a 3T MR scanner. Both femoral and acetabular cartilage layers in each joint were semi-automatically segmented on sagittal 3D high-resolution spoiled gradient echo (SPGR) images. These segmented regions of interest (ROIs) were automatically divided radially into twelve equal sub-regions (300 intervals) based on the fitted center of the femur head. The mean value of T1ρ/T2 was calculated in each sub-region after superimposing the divided cartilage contours on the MR relaxation (T1ρ/T2) maps to quantify the relaxation times. T1ρ and T2 relaxation times of the femoral cartilage were significantly higher in FAI subjects compared to healthy controls (39.9±3.3msec in FAI vs. 35.4±2.3msec in controls for T1ρ (P=0.0020); 33.9±3.1msec in FAI vs. 31.1±1.7msec in controls for T2 (P=0.0160)). Sub-regional analysis showed significantly different T1ρ and T2 relaxation times in the anterior-superior region (R9) of the hip joint cartilage between subjects with FAI and healthy subjects, suggesting possible regional differences in cartilage matrix composition between these two groups. Receiver operating characteristic (ROC) analysis showed that sub-regional analysis in femoral cartilage was more sensitive in discriminating FAI joint cartilage from that of healthy joints than global analysis of the whole region (T1ρ: area under the curve (AUC)=0.981, P=0.0001 for R9 sub-region; AUC=0.901, P=0.002 for whole region; T2: AUC=0.976, P=0.0005 for R9 sub-region; AUC=0.808, P=0.0124 for whole region). The results of this study demonstrated regional variations in hip cartilage composition using MR relaxation times (T1ρ and T2) and suggested that analysis based on local regions was more sensitive than global measures in subjects with and without FAI.

Nanosized solvent superstructures in ultramolecular aqueous dilutions: twenty years' research using water proton NMR relaxation

proton nuclear magnetic resonance (NMR) relaxation times T1, T2, T1/T2 are sensitive to motion and organization of water molecules. Especially, increase in T1/T2 reflects a higher degree of structuring. My purpose was to look at physical changes in water in ultrahigh aqueous dilutions. Samples were prepared by iterative centesimal (c) dilution with vigorous agitation, ranging between 3c and 24c (Avogadro limit 12c). Solutes were silica-lactose, histamine, manganese-lactose. Solvents were water, NaCl 0.15 M or LiCl 0.15 M. Solvents underwent strictly similar, simultaneous dilution/agitation, for each level of dilution, as controls. NMR relaxation was studied within 0.02-20 MHz. No changes were observed in controls. Increasing T1 and T1/T2 were found in dilutions, which persisted beyond 9c (manganese-lactose), 10c (histamine) and 12c (silica-lactose). For silica-lactose in LiCl, continuous decrease in T2 with increase in T1/T2 within the 12c-24c range indicated growing structuring of water despite absence of the initial solute. All changes vanished after heating/cooling. These findings were interpreted in terms of nanosized (>4-nm) supramolecular structures involving water, nanobubbles and ions, if any. Additional study of low dilutions of silica-lactose revealed increased T2 and decreased T1/T2 compared to solvent, within the 10(-3)-10(-6) range, reflecting transient solvent destructuring. This could explain findings at high dilution. Proton NMR relaxation demonstrated modifications of the solvent throughout the low to ultramolecular range of dilution. The findings suggested the existence of superstructures that originate stereospecifically around the solute after an initial destructuring of the solvent, developing more upon dilution and persisting beyond 12c.

Estimation of water retention parameters from nuclear magnetic resonance relaxation time distributions

[1] For characterizing water flow in the vadose zone, the water retention curve (WRC) of the soil must be known. Because conventional WRC measurements demand much time and effort in the laboratory, alternative methods with shortened measurement duration are desired. The WRC can be estimated, for instance, from the cumulative pore size distribution (PSD) of the investigated material. Geophysical applications of nuclear magnetic resonance (NMR) relaxometry have successfully been applied to recover PSDs of sandstones and limestones. It is therefore expected that the multiexponential analysis of the NMR signal from water-saturated loose sediments leads to a reliable estimation of the WRC. We propose an approach to estimate the WRC using the cumulative NMR relaxation time distribution and approximate it with the well-known van-Genuchten (VG) model. Thereby, the VG parameter n, which controls the curvature of the WRC, is of particular interest, because it is the essential parameter to predict the relative hydraulic conductivity. The NMR curves are calibrated with only two conventional WRC measurements, first, to determine the residual water content and, second, to define a fixed point that relates the relaxation time to a corresponding capillary pressure. We test our approach with natural and artificial soil samples and compare the NMR-based results to WRC measurements using a pressure plate apparatus and to WRC predictions from the software ROSETTA. We found that for sandy soils n can reliably be estimated with NMR, whereas for samples with clay and silt contents higher than 10% the estimation fails. This is the case when the hydraulic properties of the soil are mainly controlled by the pore constrictions. For such samples, the sensitivity of the NMR method for the pore bodies hampers a plausible WRC estimation.Citation: Costabel, S., and U. Yaramanci (2013), Estimation of water retention parameters from nuclear magnetic resonance relaxation time distributions, Water Resour. Res., 49, 2068-2079, doi:10.1002/wrcr.20207.

Changes in MR relaxation times of the meniscal body with loading: an in vivo pilot study in knee osteoarthritis

Purpose: The meniscus, a fibrocartilaginous tissue found within the knee joint, is responsible for joint congruity, shock dissipation, load transmission, lubrication, and stability of the joint. The meniscus is increasingly being recognized as an important tissue in knee osteoarthritis (OA). Recent studies have shown the potential of magnetic resonance (MR) relaxation times (T1r and T2) in studying biochemical composition of meniscus and therefore they may play a role in quantifying early meniscal degeneration and injury. One central function of themenisci is load transmission and studying the effect of acute loading on the meniscal T1r and T2 values may provide insight into the development of joint degeneration. Thus the purpose of this study is to prospectively compare changes in T1r and T2 in the meniscal body with acute loading in knees with OA and with those of age-matched healthy control menisci. Methods: Female subjects (age: 40-70 years, BMI: 20-35 kg/m2) with (KL score of 2 or 3, n 1⁄420) and without (KL score of 0, n1⁄410) radiographic evidence of knee OA, were imaged on a 3T GEMR scanner using a custommade loading device. MR images (Coronal SPGR and T1r and T2 mapping sequences) were acquired with the knee flexed at 20 with and without a compressive load of 50% of the subject's bodyweight (Figure 1) using established pulse sequences. The regions of interest (ROIs) for quantifying T1r and T2 values in the meniscus body were defined on the coronal SPGR images and superimposed over relaxation time maps. Anterior and posterior horns were not evaluated due to substantial partial volume effects in coronal images. Three different zones (outer, middle, and inner) of meniscus were defined by dividing the meniscus ROIs into three different parts with each part occupying one-third the width of the meniscus (Figure 2). After adjusting for age and BMI in the general linear regression model, repeated measures ANOVAwas used to detect significant differences in T1r and T2 with and without loading. Results: The average T1r and T2 values in all zones were significantly higher in OA patients compared with controls in unloaded condition, but not in loaded condition (Figure 3 and Figure 4). ΔT1r and ΔT2 in the outer zone of the medial meniscus in controls was significantly higher than the OA subjects (14.8% vs. 6.6%, P1⁄40.046 for ΔT1r, and 15.7% vs. 5.8%, P1⁄40.027 for ΔT2). In other zones (middle and inner), the same trend was observed but did not reach significance. Pooled data showed, significant increase in T1r of the outer zone of both medial (9.1%, P<0.0001) and lateral (6.8%, P1⁄40.014) meniscus body was observed with loading. Whereas, significant increase in T2 was observed in the outer zone of the medial meniscus (8.4%, P1⁄4 0.0003) only with minimal changes in the lateral meniscus (2.6%, P1⁄40.221). Conclusions: Elevated T1r and T2 in subjects with OA in the unloaded condition agree with literature and suggest that relaxation times of the menisci may have value in monitoring early disease. Significant relaxation time elevations in the outer portion of the meniscus with acute loading in both groupsmay reflect tissue hydration changes as the inner and middle portions of the meniscus bear load. The observation that Abstracts / Osteoarthritis an

Regional variation in T1ρ and T2 times in osteoarthritic human menisci: correlation with mechanical properties and matrix composition

Changes in T1ρ and T2 magnetic resonance relaxation times have been associated with articular cartilage degeneration, but similar relationships for meniscal tissue have not been extensively investigated. This work examined relationships between T1ρ and T2 measurements and biochemical and mechanical properties across regions of degenerate human menisci. Average T1ρ and T2 relaxation times were determined for nine regions each of seven medial and 13 lateral menisci from 14 total knee replacement patients. Sulfated glycosaminoglycan (sGAG), collagen and water contents were measured for each region. Biomechanical measurements of equilibrium compressive, dynamic compressive and dynamic shear moduli were made for anterior, central and posterior regions. T1ρ and T2 times showed similar regional patterns, with longer relaxation times in the (radially) middle region compared to the inner and outer regions. Pooled over all regions, T1ρ and T2 times showed strong correlations both with one another and with water content. Correlations with biochemical content varied depending on normalization to wet or dry mass, and both imaging parameters showed stronger correlations with collagen compared to sGAG content. Mechanical properties displayed moderate inverse correlations with increasing T1ρ and T2 times and water content. Both T1ρ and T2 relaxation times correlated strongly with water content and moderately with mechanical properties in osteoarthritic menisci, but not as strongly with sGAG or collagen contents alone. While the ability of magnetic resonance imaging (MRI) to detect early osteoarthritic changes remains the subject of investigation, these results suggest that T1ρ and T2 relaxation times have limited ability to detect compositional variations in degenerate menisci.