Toward Quantifying the Chemical Sensitivity of Nuclear Spin Surface Relaxivity in Mesoporous Media.

Low-field nuclear magnetic resonance (NMR) relaxation is a promising non-invasive technique for characterizing solid-liquid interactions within functional porous materials. However, the ability of the solid-liquid interface to enhance adsorbate relaxation rates, known as the surface relaxivity, in the case of different solvents and reagents involved in various chemical processes has yet to be evaluated in a quantitative manner. In this study, we systematically explore the surface relaxation characteristics of 10 liquid adsorbates (cyclohexane, acetone, water, and 7 alcohols, including ethylene glycol) confined within mesoporous silicas with pore sizes between 6 and 50 nm using low-field (12.7 MHz) two-dimensional 1H T1-T2 relaxation measurements. Functional-group-specific relaxation phenomena associated with the alkyl and hydroxyl groups of the confined alcohols are clearly distinguished; we report the dependence of both longitudinal (T1) and transverse (T2) relaxation rates of these 1H-bearing moieties on pore surface-to-volume ratio, facilitating the quantification and assignment of surface relaxivity values to specific functional groups within the same adsorbate molecule for the first time. We further demonstrate that alkyl group transverse surface relaxivities correlate strongly with the alkyl/hydroxyl ratio of the adsorbates assessed, providing evidence for a simple, quantitative relationship between surface relaxivity and interfacial chemistry. Overall, our observations highlight potential pitfalls in the application of NMR relaxation for the evaluation of pore size distributions using hydroxylated probe molecules, and provide motivation for the exploration of nuclear spin relaxation measurements as a route to adsorbate identity within functional porous materials.

Resilient forward osmosis membranes against microplastics fouling enhanced by MWCNTs/UiO-66-NH2 hybrid nanoparticles.

The escalating presence of microplastics (MPs) in wastewater necessitates the investigation of effective tertiary treatment process. Forward osmosis (FO) emerges as an effective non-pressurized membrane process, however, for the effective implementation of FO systems, the development of fouling-resistance FO membranes with high-performance is essential. This study focuses on the integration of MWCNT/UiO-66-NH2 as metal-organic frameworks (MOFs) and multi-wall carbon nanotubes (MWCNT) nanocomposites in thin film composite (TFC) FO membranes, harnessing the synergistic power of hybrid nanoparticles in FO membranes. The results showed that the addition of MWCNT/UiO-66-NH2 in the aqueous phase during polyamide formation changed the polyamide surface structure, and enhanced membranes' hydrophilicity by 44%. The water flux of the modified FO membrane incorporated with 0.1 wt% MWCNTs/UiO-66-NH2 increased by 67% and the reverse salt flux decreased by 22% as in comparison with the control membrane. Moreover, the modified membrane showed improved antifouling behavior against both organic foulant and MPs. The MWCNT/UiO-66-NH2 membrane experienced 35% flux decline while the control membrane experienced 65% flux decline. This proves that the integration of MWCNT/UiO-66-NH2 nanoparticles into TFC FO membranes is a viable approach in creating advanced FO membranes with high antifouling propensity with potential to be expanded further to other membrane applications.

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.

Detection of honey adulteration using benchtop 1H NMR spectroscopy.

High magnetic field NMR spectroscopy featuring the use of superconducting magnets is a powerful analytical technique for the detection of honey adulteration. Such high field NMR systems are, however, typically housed in specialised laboratories, require cryogenic coolants, and necessitate specialist training to operate. Benchtop NMR spectrometers featuring permanent magnets are, by comparison, significantly cheaper, more mobile and can be operated with minimal expertise. The lower magnetic fields used in such systems, however, result in limited spectral resolution, which diminishes their ability to perform quantitative composition analysis. These limitations may be overcome by implementing a recently developed field-invariant model-based fitting method which is defined by the underlying quantum mechanical properties of the nuclear spin system; this method is applied here to quantify the sugar composition of honey using benchtop 1H NMR (43 MHz) spectroscopy. The detection of adulteration of 26 honey samples with brown rice syrup is quantitatively demonstrated to a minimum adulterant concentration of 5 wt%. Honey adulteration with corn syrup, glucose syrup and wheat syrup was also quantitatively detected using this approach. Our NMR detection of adulteration was shown to be invariant with time over 60 days of storage.

Aqueous Solid Formation Kinetics in High-Pressure Methane at Trace Water Concentrations.

Natural gas containing trace amounts of water is frequently liquefied at conditions where aqueous solids are thermodynamically stable. However, no data are available to describe the kinetics of aqueous solid formation at these conditions. Here, we present experimental measurements of both solid formation kinetics and solid-fluid equilibrium for trace concentrations of (12 ± 0.7) ppm water in methane using a stirred, high-pressure apparatus and visual microscopy. Along isochoric pathways with cooling rates around 1 K·min-1, micron-scale aqueous solids were observed to form at subcoolings of (0.3-8.6) K, relative to an average equilibrium melting temperature of (253 ± 1.9) K at (8.9 ± 0.08) MPa; these data are consistent with predicted methane hydrate dissociation conditions within the uncertainty of both the experiment and model. The 36 measured formation events were used to construct a cumulative formation probability distribution, which was then fitted with a model from Classical Nucleation Theory, enabling the extraction of kinetic and thermodynamic nucleation parameters. While the resulting nucleation parameter values were comparable to those published for methane hydrate formation in bulk-water systems, the observed growth kinetics were distinctly different with only a small percentage of the water in the system converting into micron-scale solids over the experimental time scale. These results may help explain how cryogenic heat exchangers in liquefied natural gas facilities can operate for long periods without blockages forming despite being at very high subcoolings for aqueous solids.

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.

Synergistic effects of microplastics and organic foulants on the performance of forward osmosis membranes.

Microplastics (MPs) are emerging contaminants that are abundantly present in the influent and effluent of wastewater treatment plants (WWTPs). Forward osmosis (FO) is an advanced treatment technology with potential applications in WWTPs. The presence of MPs in WWTP effluents can contribute to FO fouling and performance deterioration. This study focuses on FO membrane fouling by MPs of different sizes, and the interactional impacts of MPs and Humic acid (HA) (as the most common organic foulant in WWTPs) on FO membrane performance. The synergistic effect of combined MPs and HA fouling is shown to cause higher flux decline for FO membranes than that of HA or MPs alone. Reverse salt flux increased in the presence of MPs, and decreased when HA was present. Further, full flux recovery was obtained for all fouled membranes after hydraulic cleaning. This indicates the efficiency of FO systems for treating wastewater with high fouling potential. This study highlights the necessity of considering MPs in studying fouling behaviour, and for mitigation strategies of membranes used in WWT. The fundamentals created here can be further extended to other membrane-assisted separation processes.

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.

Low-Field NMR Relaxation Analysis of High-Pressure Ethane Adsorption in Mesoporous Silicas.

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) 1 H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25-50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g-1 of the observed ethane capacity. NMR T2 relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis.

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.

Low-Field Functional Group Resolved Nuclear Spin Relaxation in Mesoporous Silica.

Solid-fluid interactions underpin the efficacy of functional porous materials across a diverse array of chemical reaction and separation processes. However, detailed characterization of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we report low-magnetic-field two-dimensional (2D) 1H nuclear spin relaxation measurements as a noninvasive probe of adsorbate identity and interfacial dynamics, exploring the relaxation characteristics exhibited by liquid hydrocarbon adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of this approach in distinguishing functional group-specific relaxation phenomena across a diverse range of alcohols and carboxylic acids employed as solvents, reagents, and liquid hydrogen carriers, with distinct relaxation responses assigned to the alkyl and hydroxyl moieties of each confined liquid. Uniquely, this relaxation behavior is shown to correlate with adsorbate acidity, with the observed relationship rationalized on the basis of surface-adsorbate proton-exchange dynamics. Our results demonstrate that nuclear spin relaxation provides a molecular-level perspective on sorbent/sorbate interactions, motivating the exploration of such measurements as a unique probe of adsorbate identity within optically opaque porous media.

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.

Effectiveness of bacterial cellulose in controlling purge accumulation and improving physicochemical, microbiological, and sensorial properties of vacuum-packaged beef.

The application of bacterial cellulose (BC) as a wrapping material for vacuum-packaged beef was studied and compared against unwrapped beef for up to 3 weeks. The impact of BC wrap on the weight loss, purge accumulation, and drip loss were assessed along with low-field nuclear magnetic resonance, physicochemical, microbiological, and sensorial evaluations. The BC wrap significantly (P < 0.05) reduced purge accumulation in vacuum packages which was confirmed by an increased swelling ratio and scanning electron microscopy images. Colorimetric measurements showed significantly (P < 0.05) increased redness and yellowness values in wrapped samples compared to unwrapped samples. BC wrap did not affect pH, tenderness, and odor of meat, but significantly (P < 0.05) increased lipid oxidation, and numbers of lactic acid bacteria and Brochothrix thermosphacta counts. This study shows that BC wrap has potential as a purge absorbent in vacuum packaged meat. PRACTICAL APPLICATION: Bacteria cellulose has good water holding capacity that can be utilized to absorb purge exudate from beef. It helps to improve the appearance and consequently consumer acceptance of vacuum packed beef.

Hydrate nucleation and growth on water droplets acoustically-levitated in high-pressure natural gas.

Hydrate formation was studied using water droplets acoustically levitated in high-pressure natural gas. Despite the absence of solid interfaces, the droplets' area-normalised nucleation rate was about four times faster than in steel autoclave measurements with interfacial areas roughly 200 times larger. Multiple stages of stochastic, template-free hydrate growth were observed.

Gas Hydrate Formation Probability Distributions: The Effect of Shear and Comparisons with Nucleation Theory.

Gas hydrate formation is a stochastic phenomenon of considerable significance for any risk-based approach to flow assurance in the oil and gas industry. In principle, well-established results from nucleation theory offer the prospect of predictive models for hydrate formation probability in industrial production systems. In practice, however, heuristics are relied on when estimating formation risk for a given flowline subcooling or when quantifying kinetic hydrate inhibitor (KHI) performance. Here, we present statistically significant measurements of formation probability distributions for natural gas hydrate systems under shear, which are quantitatively compared with theoretical predictions. Distributions with over 100 points were generated using low-mass, Peltier-cooled pressure cells, cycled in temperature between 40 and -5 °C at up to 2 K·min-1 and analyzed with robust algorithms that automatically identify hydrate formation and initial growth rates from dynamic pressure data. The application of shear had a significant influence on the measured distributions: at 700 rpm mass-transfer limitations were minimal, as demonstrated by the kinetic growth rates observed. The formation probability distributions measured at this shear rate had mean subcoolings consistent with theoretical predictions and steel-hydrate-water contact angles of 14-26°. However, the experimental distributions were substantially wider than predicted, suggesting that phenomena acting on macroscopic length scales are responsible for much of the observed stochastic formation. Performance tests of a KHI provided new insights into how such chemicals can reduce the risk of hydrate blockage in flowlines. Our data demonstrate that the KHI not only reduces the probability of formation (by both shifting and sharpening the distribution) but also reduces hydrate growth rates by a factor of 2.

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.