Monitoring settling of anaerobic digestates using low-field MRI profiling and NMR relaxometry measurements.

Dewatering of anaerobic digestate from red meat processing was assessed using low field MRI profiling and NMR relaxometry. Samples were flocculated using a cationic flocculant (EM640CT) at dosing range (0 to 1.6% v/v) and monitored during the initial 30 min of settling via MRI profiling to assess changes in water fraction, settling time and initial settling velocity. The profiles showed decreasing settling time and increasing initial settling velocity with increased dosing, while sample porosity was observed to increase up to the optimal dosing point (0.8% v/v). Significant increases in sample variability were observed past this point due to flocculant overdosing. The samples were then analysed in terms of turbidity and NMR relaxometry. Increasing flocculant concentration caused turbidity to decrease from 210 to 13 NTU. The relaxation rate of free water showed a strong positive correlation with turbidity. T2 peaks observed before overdosing could be assigned to different water structures (free, interstitial, vicinal and hydration). An additional T2 population emerged in the T2 distributions at the optimal dosing point. Multivariate exploratory data analysis (MEDA) showed that this T2 population from the solids layer was strongly correlated with the total solids layer height and turbidity of the watery layer. This T2 peak formation may therefore be used to study opaque flocculated solids to monitor for water structures associated with flocculant overdosing. Further studies using this technique will aim to assess the potential of low field T2 relaxometry monitoring inline before mechanical dewatering, to monitor optimal flocculant dosing during continuous operations on systems with high solids concentration.

NMR Surface Relaxivity in a Time-Dependent Porous System.

We demonstrate an unexpected decay-recovery behavior in the time-dependent ^{1}H NMR relaxation times of water confined within a hydrating porous material. Our observations are rationalized by considering the combined effects of decreasing material pore size and evolving interfacial chemistry, which facilitate a transition between surface-limited and diffusion-limited relaxation regimes. Such behavior necessitates the realization of temporally evolving surface relaxivity, highlighting potential caveats in the classical interpretation of NMR relaxation data obtained from complex porous systems.

Monitoring residual fouling after cleaning of multi-fiber membrane modules fiber-by-fiber using non-invasive MRI monitoring.

In this study non-invasive low field magnetic resonance imaging (MRI) technology was used to monitor fouling induced changes in fiber-by-fiber hydrodynamics inside a multi-fiber hollow fiber membrane module containing 401 fibers. Using structural and velocity images the fouling evolution of these membrane modules were shown to exhibit distinct trends in fiber-by-fiber volumetric flow, with increasing fouling causing a decrease in the number of flow active fibers. This study shows that the fouling rate is not evenly distributed over the parallel fibers, which results in a broadening of the fiber to fiber flowrate distribution. During cleaning, this distribution is initially broadened further, as relatively clean fibers are cleaned more rapidly compared to clogged fibers. By tracking the volumetric flow rate of individual fibers inside the modules during the fouling-cleaning cycle it was possible to observe a fouling memory-like effect with residual fouling occurring preferentially at the outer edge of the fiber bundle during repeated fouling-cleaning cycle. These results demonstrate the ability of MRI velocity imaging to quantitatively monitor these effects which are important when testing the effectiveness of cleaning protocols due to the long term effect that residual fouling and memory-like effect may have on the operation of membrane modules.

Quantifying motional dynamics in nuclear magnetic resonance logging.

The motional dynamics of nuclear magnetic resonance (NMR) logging tools can significantly influence the measurement performance of such tools. NMR logging is used for geophysical evaluation in geological environments, primarily quantifying formation porosity and fluid volumes, as well as providing a qualitative estimation of permeability. NMR logging tools are conveyed via two main mechanisms; wireline logging and logging while drilling (LWD). We conduct detailed simulations to quantify the impact of tool motion on NMR measurements during logging. This involves conducting electromagnetic simulations which quantify the magnetic fields generated by a logging tool, and subsequently introducing motion profiles within the relevant spin dynamic calculations. This enables tool motional dynamics to be imposed on the signal acquisition. Several movement profiles are considered: linear axial movement to replicate wireline logging tool motion, as well as axial harmonic and lateral harmonic movement to simulate the shocks and vibrations experienced during logging while drilling. Lateral motion is observed to cause a greater degree of signal attenuation relative to axial motion due to the cylindrical shape of the excited volume. The magnitude of motion (e.g. the velocity of linear motion or the amplitude of harmonic motion) is demonstrated to increase the severity of signal attenuation, as expected. However, the frequency of harmonic motion demonstrates a more complex effect on the measured signal. The harmonic interaction between the motion frequency and measurement frequency (determined by the echo spacing) can cause wave interference which results in enhanced or diminished signal attenuation. Finally, we demonstrate that reducing both the magnetic field gradient as well as the echo spacing reduce the degree of signal attenuation observed during measurement. The results presented in this work demonstrate how the optimisation of key design parameters can be used to control the sensitivity of NMR logging tools towards motion.

Controlling the hydraulic resistance of membrane biofilms by engineering biofilm physical structure.

The application of membrane technology for water treatment and reuse is hampered by the development of a microbial biofilm. Biofilm growth in micro-and ultrafiltration (MF/UF) membrane modules, on both the membrane surface and feed spacer, can form a secondary membrane and exert resistance to permeation and crossflow, increasing energy demand and decreasing permeate quantity and quality. In recent years, exhaustive efforts were made to understand the chemical, structural and hydraulic characteristics of membrane biofilms. In this review, we critically assess which specific structural features of membrane biofilms exert resistance to forced water passage in MF/UF membranes systems applied to water and wastewater treatment, and how biofilm physical structure can be engineered by process operation to impose less hydraulic resistance ("below-the-pain threshold"). Counter-intuitively, biofilms with greater thickness do not always cause a higher hydraulic resistance than thinner biofilms. Dense biofilms, however, had consistently higher hydraulic resistances compared to less dense biofilms. The mechanism by which density exerts hydraulic resistance is reported in the literature to be dependant on the biofilms' internal packing structure and EPS chemical composition (e.g., porosity, polymer concentration). Current reports of internal porosity in membrane biofilms are not supported by adequate experimental evidence or by a reliable methodology, limiting a unified understanding of biofilm internal structure. Identifying the dependency of hydraulic resistance on biofilm density invites efforts to control the hydraulic resistance of membrane biofilms by engineering internal biofilm structure. Regulation of biofilm internal structure is possible by alteration of key determinants such as feed water nutrient composition/concentration, hydraulic shear stress and resistance and can engineer biofilm structural development to decrease density and therein hydraulic resistance. Future efforts should seek to determine the extent to which the concept of "biofilm engineering" can be extended to other biofilm parameters such as mechanical stability and the implication for biofilm control/removal in engineered water systems (e.g., pipelines and/or, cooling towers) susceptible to biofouling.

Novel Magnetic Resonance Measurements of Fouling in Operating Spiral Wound Reverse Osmosis Membrane Modules.

A novel magnetic resonance measurement (MRM) protocol for non-invasive monitoring of fouling in spiral wound reverse osmosis (SWRO) membrane modules is demonstrated. Sodium alginate was used to progressively foul a commercial SWRO membrane at industrially relevant operating conditions in a circulating flow loop. The MRM protocol showcased the following: (i) earlier, more sensitive detection and quantification of fouling in the membrane module compared to feed-channel pressure drop. This was achieved using appropriate detection of the total nuclear magnetic resonance (NMR) signal. (ii) 2D cross-sectional imaging of the location of the accumulated foulant material; this was preferentially located adjacent to the membrane spacer sheet nodes, which was subsequently confirmed by a module autopsy. This image contrast, which could also readily differentiate the membrane, feed spacer and permeate spacer regions, was realised based on differences in the NMR relaxation parameter, T2,eff. (iii) High frequency acquisition of 2D cross-sectional velocity images of the module revealing very localised flow channelling in response to gradual foulant accumulation which impacted significantly on the flow pattern within the central permeate tube. Collectively this NMR/MRI measurement protocol provides a powerful analysis tool for the evolution of fouling in such complex modules, thus ultimately enabling more informed module design.

Low-field NMR relaxation-exchange measurements for the study of gas admission in microporous solids.

Understanding the uptake and storage of gases by microporous materials is important for our future energy security. As such, we demonstrate here the application of two-dimensional NMR relaxation experiments for probing the admission and corresponding exchange dynamics of methane within microporous zeolites. Specifically, we report low-field (12.7 MHz) 1H NMR relaxation-exchange correlation measurements of methane within commercial LTA zeolites (3A and 4A) at 25 and 35 bar and ambient temperature. Our results demonstrate the clear identification of bulk-pore and pore-pore exchange processes within zeolite 4A, facilitating the calculation and comparison of effective exchange rate dynamics across varying diffusion length scales and gas pressures. Additional data acquired for zeolite 3A reveals the sensitivity of NMR relaxation phenomena to size-exclusive gas admission phenomena, illustrating the potential of benchtop NMR protocols for material screening applications.

Quantitative velocity distributions via nuclear magnetic resonance flow metering.

We demonstrate the use of Tikhonov regularisation as a data inversion technique to determine the velocity distributions of flowing liquid streams. Regularisation is applied to the signal produced by a nuclear magnetic resonance (NMR) flow measurement system consisting of a pre-polarising permanent magnet located upstream of an Earth's magnetic field NMR detection coil. A simple free induction decay (FID) NMR signal is measured for the flowing stream in what is effectively a 'time-of-flight' measurement. The FID signal is then modelled as a function of fluid velocity and acquisition time, enabling determination of the velocity probability distributions via regularisation. The mean values of these velocity distributions were successfully validated against in-line rotameters. The ability to quantify multi-modal velocity distributions was also demonstrated using a two-pipe system.

Shear-induced emulsion droplet diffusion studies using NMR.

HYPOTHESIS: Shear-induced droplet diffusion of flowing hard spheres is relatively well understood and has been extensively studied both experimentally and via simulations. The same however is not true of soft spheres, specifically emulsions, despite their broad and extensive industrial relevance. Here we seek to demonstrate that appropriate NMR techniques can be used to quantitatively measure shear-induced droplet diffusion. Limited literature indicates that dilute dispersions of soft spheres experience significantly larger shear-induced droplet diffusion relative to otherwise equivalent hard sphere suspensions. Here we explore whether this effect persists to high concentrations. EXPERIMENTS: Nuclear Magnetic Resonance (NMR) pulsed field gradient (PFG) techniques were used to measure shear-induced droplet diffusion for capillary flow of various water-in-oil (w/o) emulsions in a direction transverse to flow. Two adaptations were necessary - the acquired signal was analyzed so as to quantitatively distinguish restricted molecular diffusion within the emulsion droplets from shear-induced diffusion of the droplets, whilst flow-compensated PFG pulse sequences were shown to be necessary to account for any erroneous effects due to flow. A range of w/o emulsions were considered to enable measurement of shear-induced droplet diffusion as a function of both water content and mean shear rate. The surfactant content of these emulsions was adjusted such that they presented similar (stationary) emulsion droplet size distributions (DSD) which were also measured using NMR PFG techniques. FINDINGS: The droplet shear-induced diffusion data for the emulsion systems were compared against relevant results from the literature. Consistent with predictions for dilute systems, significantly greater droplet diffusion was measured relative to hard sphere suspensions at all concentrations, and a quadratic dependence was found between droplet diffusion and mean droplet size. For more concentrated emulsions, a peak in the droplet diffusion-concentration relationship was observed for the first time in emulsions, prior to the onset of emulsion inversion.

Hydrate Shell Growth Measured Using NMR.

Benchtop nuclear magnetic resonance (NMR) pulsed field gradient (PFG) and relaxation measurements were used to monitor the clathrate hydrate shell growth occurring in water droplets dispersed in a continuous cyclopentane phase. These techniques allowed the growth of hydrate inside the opaque exterior shell to be monitored and, hence, information about the evolution of the shell's morphology to be deduced. NMR relaxation measurements were primarily used to monitor the hydrate shell growth kinetics, while PFG NMR diffusion experiments were used to determine the nominal droplet size distribution (DSD) of the unconverted water inside the shell core. A comparison of mean droplet sizes obtained directly via PFG NMR and independently deduced from relaxation measurements showed that the assumption of the shell model-a perfect spherical core of unconverted water-for these hydrate droplet systems is correct, but only after approximately 24 h of shell growth. Initially, hydrate growth is faster and heat-transfer-limited, leading to porous shells with surface areas larger than that of spheres with equivalent volumes. Subsequently, the hydrate growth rate becomes mass-transfer-limited, and the shells become thicker, spherical, and less porous.

Earth's field NMR flow meter: preliminary quantitative measurements.

In this paper we demonstrate the use of Earth's field NMR (EF NMR) combined with a pre-polarising permanent magnet for measuring fast fluid velocities. This time of flight measurement protocol has a considerable history in the literature; here we demonstrate that it is quantitative when employing the Earth's magnetic field for signal detection. NMR signal intensities are measured as a function of flow rate (0-1m/s) and separation distance between the permanent magnet and the EF NMR signal detection. These data are quantitatively described by a flow model, ultimately featuring no free parameters, that accounts for NMR signal modulation due to residence time inside the pre-polarising magnet, between the pre-polarising magnet and the detection RF coil and inside the detection coil respectively. The methodology is subsequently demonstrated with a metallic pipe in the pre-polarising region.

Determination of mean droplet sizes of water-in-oil emulsions using an Earth's field NMR instrument.

The use of the Earth's magnetic field (EF) to conduct nuclear magnetic resonance (NMR) experiments has a long history with a growing list of applications (e.g. ground water detection, diffusion measurements of Antarctic sea ice). In this paper we explore whether EFNMR can be used to accurately and practically measure the mean droplet size () of water-in-oil emulsions (paraffin and crude oil). We use both pulsed field gradient (PFG) measurements of restricted self-diffusion and T2 relaxometry, as appropriate. T2 relaxometry allows the extension of droplet sizing ability below the limits set by the available magnetic field gradient strength of the EFNMR apparatus. A commercially available bench-top NMR spectrometer is used to verify the results obtained using the EFNMR instrument, with good agreement within experimental error, seen between the two instruments. These results open the potential for further investigation of the application of EFNMR for emulsion droplet sizing.

NMR measurement of hydrodynamic dispersion in porous media subject to biofilm mediated precipitation reactions.

Noninvasive measurements of hydrodynamic dispersion by nuclear magnetic resonance (NMR) are made in a model porous system before and after a biologically mediated precipitation reaction. Traditional magnetic resonance imaging (MRI) was unable to detect the small scale changes in pore structure visualized during light microscopy analysis after destructive sampling of the porous medium. However, pulse gradient spin echo nuclear magnetic resonance (PGSE NMR) measurements clearly indicated a change in hydrodynamics including increased pore scale mixing. These changes were detected through time-dependent measurement of the propagator by PGSE NMR. The dynamics indicate an increased pore scale mixing which alters the preasymptotic approach to asymptotic Gaussian dynamics governed by the advection diffusion equation. The methods described here can be used in the future to directly measure the transport of solutes in biomineral-affected porous media and contribute towards reactive transport models, which take into account the influence of pore scale changes in hydrodynamics.

NMR measurement of the transport dynamics of colloidal particles in an open cell polymer foam porous media.

The transport of model hard sphere core shell colloidal particles under flow through a random open-cell solid polymer foam is studied using nuclear magnetic resonance. Unique data on the scale dependent dynamics of the colloidal particle and suspending fluid phase are obtained using spectral chemical resolution. The dynamics of each phase are shown to differ from one another dependent on the displacement length and time scale of the measurement. The data is interpreted in the context of classic hydrodynamic dispersion theory and mechanisms of transport for each phase.

Dynamics of the solid and liquid phases in dilute sheared Brownian suspensions: irreversibility and particle migration.

Magnetic resonance measurements of migration and irreversible dynamics in the capillary shear flow of a Brownian suspension are presented. The results demonstrate the presence of phenomena typically associated with concentrated noncolloidal systems and indicate the role of many body hydrodynamics in dilute Brownian suspension transport. The application of concepts from chaos theory and nonequilibrium statistical mechanics is demonstrated.