Non-steady State Research Articles

(Invited) Characterization of Charge Transfer and Recombination Processes at Metal Oxide Semiconductors for Solar Water Splitting

Metal oxide (MO) semiconductors based on abundant, low-cost materials are attractive for application in photoelectrochemical water splitting systems related to their inherent stability, specifically against oxidation. In addition, these materials provide a wide-ranging versatility in terms of composition, physical and chemical properties, and configuration of multi-component architectures. The semiconducting MO must at least comply with three requirements: (i) absorb sunlight efficiently; (ii) the valence and conduction band edges must be situated at the appropriate energies; and (iii) the electrochemical reaction must have favorable kinetics compared with charge separation, transport and recombination kinetics. Many systems have been evaluated for photo-oxidation of water in the past 10 years, with some of the more popular materials being Fe2O3, WO3, BiVO4, TiO2, etc.In order to improve the efficiency of a solar water splitting system, the specific loss mechanisms need to be elucidated; based on these insights strategies may then be developed to improve performance. However, it is not straightforward to determine the precise loss mechanisms and generally non-steady state methods need to be applied in combination with steady-state techniques. Intensity-modulated photocurrent spectroscopy (IMPS) is a powerful technique to study the carrier dynamics in a photoelectrochemical cell: the photocurrent admittance corresponds to the frequency-dependent external quantum efficiency, and time constants for charge separation, charge transfer and surface recombination may be deduced. The kinetic model applicable to the specific system determines the interpretation of the results. On the other hand, theoretical modeling is a very powerful method to validate the interpretation of the results, and to complement the experimental studies in order to obtain a clear picture of the dominant processes and effects.In this presentation, the results from IMPS studies on a variety of systems will be discussed and strategies to improve performance are presented and tested, both experimentally and theoretically: (i) planar, compact WO3 / BiVO4 heterojunction systems are compared with nanorod array WO3 / BiVO4 heterojunctions, with and without a hole scavenger; (ii) CuBi2O4 with and without catalysts and an alternative electron acceptor; and (iii) specific examples of other materials to highlight the proposed interpretations. The results are compared with calculations of the IMPS response using a classic kinetic model and a continuity equation approach in order to incorporate the effects of charge transport and electric field within the electrode.The authors gratefully acknowledge funding from CONACYT, SENER, and CICY through the Renewable Energy Laboratory of South East Mexico (LENERSE; Project 254667; SP-4), and CONACYT under the Basic Sciences (CB) project A1-S-28734. We also thank the Ministerio de Ciencia e Innovación, the Agencia Estatal de Investigación (AEI), and the European Regional Development Fund of the European Union through Project PID2019-110430GB-C22. AR thanks the Spanish Ministry of Education, Culture and Sports via a PhD grant (FPU2017-03684). Finally, we would like thank Dr. Antonio Zapien and the NANOMXCN initiative to foment scientific collaboration between Mexico and China for support.

Supervised and unsupervised learning of directed percolation.

Machine learning (ML) has been well applied to studying equilibrium phase transition models by accurately predicating critical thresholds and some critical exponents. Difficulty will be raised, however, for integrating ML into nonequilibrium phase transitions. The extra dimension in a given nonequilibrium system, namely time, can greatly slow down the procedure toward the steady state. In this paper we find that by using some simple techniques of ML, non-steady-state configurations of directed percolation (DP) suffice to capture its essential critical behaviors in both (1+1) and (2+1) dimensions. With the supervised learning method, the framework of our binary classification neural networks can identify the phase transition threshold, as well as the spatial and temporal correlation exponents. The characteristic time t_{c}, specifying the transition from active phases to absorbing ones, is also a major product of the learning. Moreover, we employ the convolutional autoencoder, an unsupervised learning technique, to extract dimensionality reduction representations and cluster configurations of (1+1) bond DP. It is quite appealing that such a method can yield a reasonable estimation of the critical point.

PET-ABC: fully Bayesian likelihood-free inference for kinetic models

Aims. We describe an intuitive, easy to use method called PET-ABC that enables full Bayesian statistical inference from single subject dynamic PET data. The performance of PET-ABC was compared with weighted non-linear least squares (WNLS) in terms of reliability of kinetic parameter estimation and statistical power for model selection. Methods. Dynamic PET data based on 1-tissue and 2-tissue compartmental models were simulated with 2 noise models and 3 noise levels. PET-ABC was used to evaluate the reliability of parameter estimates under each condition. It was also used to perform model selection for a simulated noisy dataset composed of a mixture of 1- and 2-tissue compartment kinetics. Finally, PET-ABC was used to analyze a non-steady state dynamic [11C] raclopride study performed on a fully conscious rat administered either 2 mg.kg−1 amphetamine or saline 20 min after tracer injection. Results. PET-ABC yielded posterior point estimates for model parameters with smaller variance than WNLS, as well as probability density functions indicating confidence intervals for those estimates. It successfully identified the superiority of a 2-tissue compartment model to fit the simulated mixed model data. For the drug challenge study, the post observation probability of striatal displacement of the PET signal was 0.9 for amphetamine and approximately 0 for saline, indicating a high probability of amphetamine-induced endogenous dopamine release in the striatum. PET-ABC also demonstrated superior statistical power to WNLS (0.87 versus 0.09) for selecting the correct model in a simulated ligand displacement study. Conclusions. PET-ABC is a simple and intuitive method that provides complete Bayesian statistical analysis of single subject dynamic PET data, including the extent to which model parameter estimates and model choice are supported by the data. Software for PET-ABC is freely available as part of the PETabc package https://github.com/cgrazian/PETabc.

Rapid recovery of normal gill morphology and blood physiology in brown trout (<em>Salmo trutta</em>) after short-term exposure to toxic concentrations of aqueous aluminium under non-steady state chemical conditions

Freshwater acidification is characterised by elevated concentrations of aqueous aluminium. Global emissions of acidifying agents are reduced due to international agreements, and freshwater acidification has shifted from chronic to a more episodic character. The recovery of fish populations in acidified areas is likely to depend on the individual’s ability to recover from short-time aluminium exposures. We exposed brown trout (Salmo trutta) to an Al-rich medium, nominal concentration 600 µg L–1, for 0.5, 2, 6, 8 and 11 hours, before transfer to circumneutral Al-poor water for recovery. As controls, fish were either exposed for 11 hours to an acidified Al-poor medium or to untreated water. Some mortality during the first 24 hours of the recovery period occurred in fish exposed for 11, 8 and 6 hours to aluminium. No mortality during recovery was observed in the remaining groups. Aluminium exposure led to increased haematocrit and plasma lactate concentration, decreased plasma chloride concentration, deposition of aluminium on gill surfaces, and morphological alteration of the gill structures. The responses depended on exposure time. Aluminium deposited on the gill disappeared and plasma lactate levels were at control levels after 1 day in the recovery water, while haematocrit and plasma chloride levels were at control levels after 14 days of recovery. Gills in fish exposed to aluminium for 11 hours were almost fully recovered after 14 days. We conclude that the toxic response in brown trout exposed to an acutely toxic aluminium challenge is reversible. Moreover, the first 24 hours after aluminium exposures is the most critical period for the fish recovery. Further, it takes no more than 14 days for brown trout to fully recover from an acute toxic aluminium exposure, and only 1 day if the aluminium challenge is moderate.

The Urine Anion Gap: Common Misconceptions.

Two papers, one in 1986 and another one in 1988, reported a strong inverse correlation between urinary anion gap (UAG) and urine ammonia excretion (UNH4) in patients with metabolic acidosis and postulated that UAG could be used as an indirect measure of UNH4 This postulation has persisted until now and is widely accepted. In this review, we discuss factors regulating UAG and examine published evidence to uncover errors in the postulate and the design of the original studies. The essential fact is that, in the steady state, UAG reflects intake of Na, K, and Cl. Discrepancy between intake and urinary output of these electrolytes (i.e, UAG) indicates selective extrarenal loss of these electrolytes or nonsteady state. UNH4 excretion, which depends, in the absence of renal dysfunction, mainly on the daily acid load, has no consistent relationship to UAG either theoretically or in reality. Any correlation between UAG and UNH4, when observed, was a fortuitous correlation and cannot be extrapolated to other situations. Furthermore, the normal value of UAG has greatly increased over the past few decades, mainly due to increases in dietary intake of potassium and widespread use of sodium salts with anions other than chloride as food additives. The higher normal values of UAG must be taken into consideration in interpreting UAG.

Oxygen Uptake and Near Infrared Spectroscopy Responses during Heavy Intensity Pseudorandom Binary Sequence Exercise

Activities of daily living are characterized by continuous changes in exercise intensity and duration resulting in many abrupt changes in metabolic demand. The ability to readily meet these demands is described by the rate of adaptation in oxygen uptake measured at either the mouth (VO2p) or at the site of active muscle. Many studies have used a single step transition to assess this rate of adaptation. However, a continually changing exercise, such as a pseudorandom binary sequence (PRBS) protocol, provides more transition phases to analyze. We examined the VO2p and microvascular oxygenation responses using near infrared spectroscopy (NIRS) during PRBS exercise. Five healthy males (30 ± 6 yrs, 83.4 ± 20.9 kg, VO2pk, 38.9 ± 5.9 mL/kg/min; mean ± SD) completed a ramp exercise to fatigue for the determination of the lactate threshold (LT) and peak VO2p (VO2pk). Each bout of PRBS exercise transitioned from a baseline of 20 W to a WR corresponding to either 90% of LT (MOD, 100 ± 7 W)) or to a WR at 40% of the difference between LT and VO2pk (HVY, 173 ± 13 W). The PRBS exercise consisted of 30 units of 15 s that alternated between BSL and the higher WR in a pseudorandom pattern; the pattern was repeated 3 times. VO2p was measured breath-by-breath using a metabolic cart and interpolated to 1 s intervals. For each subject and WR, the 3 repetitions for each trial were ensembled averaged yielding a single 450 s response. Changes in hemoglobin oxygenation (deoxy-[Hb+Mb]) and total hemoglobin concentration ([THC]) were measured from the vastus lateralis (VL) using frequency-domain NIRS. Data were collected at 1 Hz and ensembled averaged to yield a single 450 s response. VO2p and deoxy-[Hb+Mb] responses were transformed into the frequency domain and analyzed using standard approaches and the mean-normalized gain (MNG). The harmonic amplitudes (Amph) for VO2p/WR were lower (p<0.05) during HVY at 0.0067 Hz (Mod, 56.9 ± 13.0 %; HVY, 49.3 ± 6.8 %), 0.011 Hz (Mod, 37.6 ± 17.0 %, HVY: 25.8 ± 5.7 %) and 0.013 Hz (Mod, 33.2 ± 12.8 %; HVY, 15.8 ± 10.2 %). The Amph for deoxy-[Hb+Mb]/WR were lower (p<0.05) for VO­2p/WR in HVY compared to MOD (Mod, 39.5 ± 6.0 %; HVY, 30.2 ± 3.9 %). MNG was also lower (p<0.05) for deoxy-[Hb+Mb]/WR in HVY compared to MOD (Mod, 77.4 ± 26.6 %; HVY, 47.3 ± 10.0 %). The VO2p and deoxy-[Hb+Mb] responses from a PRBS trial represent the responses to individual sinusoidal inputs at each frequency tested. The normalized Amph and MNG measured in the current study described the temporal dynamics of the variables of interest (i.e., VO2p and deoxy-[Hb+Mb]). The results of the current study showed a significant decrease in both normalized Amph and MNG for VO2p and deoxy-[Hb+Mb] suggesting that exercise performed above the LT results in a slowing of both the VO2p and microvascular deoxy-[Hb+Mb] responses. These findings are consistent with previous studies demonstrating a slowing of VO2p above the LT. Compared to studies using a single step protocol, responses to PRBS protocols include many transition periods to identify potential control mechanisms that are more discernable during non-steady state exercise.

Determining the effect of fuzziness in the parameters of a linear dynamic system on its stability

This paper considers a relevant issue related to the influence exerted by the fuzziness in linear dynamic system parameters on its stability. It is known that the properties of automated control systems can change under the influence of parametric disturbances. To describe the change in such properties of the system, the concept of roughness is used. It should be noted that taking into consideration the fuzziness in the parameters of mathematical models could make it possible at the design stage to assess all the risks that may arise as a result of an uncontrolled change in the parameters of dynamic systems during their operation. To prevent negative consequences due to variance in the parameters of mathematical models, automated control systems are designed on the basis of the requirement for ensuring a certain margin of stability of the system in terms of its amplitude and phase. At the same time, it remains an open question whether such a system would satisfy the conditions of roughness. Parameters of the mathematical model of a system are considered as fuzzy quantities that have a triangular membership function. This function is inconvenient for practical use, so it is approximated by the Gaussian function. That has made it possible to obtain formulas for calculating the characteristic polynomial and the transfer function of the open system, taking into consideration the fuzziness of their parameters. When investigating the system according to Mikhailov’s criterion, it was established that the dynamic system retains stability in the case when the parameters of the characteristic equation are considered as fuzzy quantities. It has been determined that the quality of the system significantly deteriorated in terms of its stability that could make it enter a non-steady state. When using the Nyquist criterion, it was established that taking into consideration the fuzziness in the parameters of the transfer function did not affect the stability of the closed system but there was a noticeable decrease in the system stability reserve both in terms of phase and amplitude. The relative decrease in the margin of stability for amplitude was 16 %, and for phase ‒ 17.4 %.

Winter CH4 oxidation in cold-temperate grassland soils of northern Japan: 222Rn as a proxy for the validation of CH4 diffusivity

Amidst changing seasonal snow-covered periods and extents in northern high latitude regions, winter CH4 oxidation is susceptible to drastic climate change, all of which modulates an accurate assessment of regional carbon balance. The importance of winter CH4 oxidation to the soils in these regions has previously been recognized; in this study, concentrations of CH4 and 222Rn were observed in the snowpack and underlying cold temperate soils during the winters of 1995/96 and 1996/97. These observations were carried out in order to 1) validate the 222Rn tracer as a proxy for variations in CH4 diffusivity within a snowpack containing many seasonal ice lenses, and to 2) estimate winter CH4 oxidation through the snowpack to the soils. Winter CH4 oxidations estimated by snow density (method 1); using the 222Rn tracer under steady (method 2) and non-steady (method 3) conditions; and using a static chamber (method 4) during the winter of 1996/97 yielded 16.7 ± 6.3; 8.2 ± 2.9; 9.8 ± 7.4; and 4.5 ± 2.5 mg CH4–C m−2, respectively. These results suggest that contributions from average CH4 oxidation represent 23.3% (range: 12.7–35.1%) of the annual CH4 oxidation into cold temperate soils. Wintertime CH4 oxidation significantly reflects temporal variation in the snowpack, demonstrating that soil temperature depends on snow cover, and that a threshold snow depth of 40 cm does not prevent, but rather promotes, atmospheric CH4 oxidation through snowpack to the soils. These findings demonstrate that the 222Rn tracer was useful for estimating winter CH4 diffusivity and oxidation, using a one-dimensional vertical diffusion box model in cold temperate soils in Japan during multiple snow-covered seasons.

Determination of penicillamine, tiopronin and glutathione in pharmaceutical formulations by kinetic spectrophotometry.

A novel and simple method for the determination of penicillamine (PEN), tiopronin (mercaptopropionyl glycine, MPG) and glutathione (GSH) in pharmaceutical formulations by kinetic spectrophotometry has been developed and validated. It is based on the redox reaction where the thiol compound (RSH) reduces CuII-neocuproine complex to CuI-neocuproine complex. The non-steady state signal of the formed CuI- neocuproine complex is measured at 458 nm. The initial rate and fixed time (at 1 min) methods were validated. The calibration graph was linear in the concentration range from 8.0 × 10‒7 to 8.0 × 10‒5 mol L-1 for the initial rate method and from 6.0 × 10‒7 to 6.0 × 10-5 mol L-1 for the fixed time method, with the detection limits of 2.4 × 10-7 and 1.4 × 10‒7 mol L-1, resp. Levels of PEN, MPG and GSH in pharmaceutical formulations were successfully assayed by both methods. The advantages of the presented methods include sensitivity, short analysis time, ease of application and low cost.

Core‐Shell Nanostructures: Dynamic Control of Orthogonal Upconversion in Migratory Core–Shell Nanostructure toward Information Security (Adv. Funct. Mater. 14/2021)

In article number 2009796, Bo Zhou and co-workers propose a novel simple migratory core–shell conceptual model for orthogonal upconversion. The red-to-green switchable output is easily achieved by dynamic control of the upconversion by altering the excitation wavelengths (e.g., 980/1530 nm) or using the non-steady state excitation, showing great promise in the multi-level information security.

Insights into gas migration behavior in saturated GMZ bentonite under flexible constraint conditions

Gas migration behavior of bentonite-based buffer/backfill materials is one of the most important issues for safety assessment of deep geological repository for disposal of high-level radioactive wastes. In this paper, a series of gas injection tests were conducted on water-saturated bentonite specimens under stepwise increasing gas injection pressure and a flexible boundary condition. Prior to the gas injection tests, the steady state water permeability (stst kw) was determined by the water injection tests with deionized water and the stst kw values obtained were in an order of magnitude of 10-19-10-20 m2, which were slightly lower than the non-steady state ones calculated from the results obtained at the initial stage of gas injection tests. The effective gas permeability measured before and after gas breakthrough on the initially water-saturated bentonite specimens with different dry densities ranges between 5.45 × 10-25 m2 to 2.76 × 10-22 m2. The Peclet number (Pe) was adopted to determine the relative importance of advective gas transport (pressure-driven gas flow) to diffusive gas transport through saturated bentonite specimens. Calculation shows that the Pe values are significantly lower than 1, indicating the dominant role of gas diffusion across the specimens before and after gas breakthrough. As dry density of the specimen increases from 1.3 g/cm3 to 1.7 g/cm3, the gas breakthrough pressure increases from 4.92 MPa to 8.68 MPa. Meanwhile, the residual pressure differences measured after gas breakthrough ranges from 4.04 MPa to 7.88 MPa for specimens with different dry densities. A slight decrease of water content of the specimens experienced gas injection tests and a stable increase of specimen volume at the breakthrough indicate that both the displacement of water from interconnected pathways (capillary effect) and the pathway dilation (mechanical effect) play important roles in gas breakthrough for specimen tested under flexible conditions.

Kinetic Glomerular Filtration Rate Equations in Patients With Shock: Comparison With the Iohexol-Based Gold-Standard Method.

Static glomerular filtration rate formulas are not suitable for critically ill patients because of nonsteady state glomerular filtration rate and variation in the volume of distribution. Kinetic glomerular filtration rate formulas remain to be evaluated against a gold standard. We assessed the most accurate kinetic glomerular filtration rate formula as compared to iohexol clearance among patients with shock. Retrospective multicentric study. Three French ICUs in tertiary teaching hospitals. Fifty-seven patients within the first 12 hours of shock. On day 1, we compared kinetic glomerular filtration rate formulas with iohexol clearance, with or without creatinine concentration correction according to changes in volume of distribution and ideal body weight. We analyzed three static glomerular filtration rate formulas (Cockcroft and Gault, modification of diet in renal disease, and Chronic Kidney Disease-Epidemiology Collaboration), urinary creatinine clearance, and seven kinetic glomerular filtration rate formulas (Jelliffe, Chen, Chiou and Hsu, Moran and Myers, Yashiro, Seelhammer, and Brater). We evaluated 33 variants of these formulas after applying corrective factors. The bias ranged from 12 to 47 mL/min/1.73 m2. Only the Yashiro equation had a lower bias than urinary creatinine clearance before applying corrective factors (15 vs 20 mL/min/1.73 m2). The corrected Moran and Myers formula had the best mean bias, 12 mL/min/1.73 m2, but wide limits of agreement (-50 to 73). The corrected Moran and Myers value was within 30% of iohexol-clearance-measured glomerular filtration rate for 27 patients (47.4%) and was within 10% for nine patients (15.8%); other formulas showed even worse accuracy. Kinetic glomerular filtration rate equations are not accurate enough for glomerular filtration rate estimation in the first hours of shock, when glomerular filtration rate is greatly decreased. They can both under- or overestimate glomerular filtration rate, with a trend to overestimation. Applying corrective factors to creatinine concentration or volume of distribution did not improve accuracy sufficiently to make these formulas reliable. Clinicians should not use kinetic glomerular filtration rate equations to estimate glomerular filtration rate in patients with shock.

Investigation of design strategies and quantification of energy flexibility in buildings: A case-study in southern Italy

The need for nearly (net) zero energy buildings in the current European landscape does not merely refer to energy balances: the aim to investigate the interaction between generation and load and find sources of technical-economic energy efficiency is marking the rise in interest throughout research and practice of energy flexibility solutions in buildings. In this regard, the study aims at enhancing the energy flexibility of a building in southern Italy through Rule-Based Control algorithms for the control of the space heating system and the charge and discharge of an electricity storage. The influence of electricity pricing and the thermal comfort conditions on flexibility is also investigated. The study is based on a validated thermal building model in non-steady state conditions developed in TRNSYS environment. New key performance indicators are proposed and tested to contribute to a clearer quantification of energy flexibility in the building design phase. The main results show the effectiveness of flexible control algorithms both from an economic and environmental perspective: operation costs are reduced by 10%, while CO2 emissions can be reduced by up to 79%. The study highlights the potential of energy flexibility approaches in the Mediterranean area, where lessons learned can be exported. The novel contribution of the study lies in the development of innovative energy flexibility key performance indicators as well as in the generation of site specific data for Mediterranean Europe.

The Thermal Diffusivity of Sedimentary Rocks: Empirical Validation of a Physically Based α − φ Relation

AbstractUnderstanding the thermal behavior of nonsteady state subsurface geosystems, when temperature changes over time, requires knowledge on the speed of heat propagation and, thus, of the rock's thermal diffusivity as essential thermo‐physical parameter. Mixing models are commonly used to describe thermo‐physical properties of polymineralic rocks. A thermal diffusivity‐porosity relation is known from literature that incorporates common mixing models into the heat equation and properly works for unconsolidated, clastic clayey, and sandy marine sediments of high porosity (35%–80%). We have proofed the relation's applicability for consolidated, isotropic sedimentary rocks of low porosity (&lt;35%). The performance of this approach was evaluated for consolidated quartz‐dominated sandstones containing air, water, and heptane as pore‐ and/or fracture‐filling medium. For these rocks, the reliability of the relation was confirmed for the entire range of porosity and all three media, with water‐saturated rocks displaying an almost perfect fit between measured and modeled thermal diffusivity. Additional measurements conducted on a larger suite of low‐porous siliciclastic and carbonate rocks imply that it is also suitable to acceptably good to infer the thermal diffusivity of mineralogically more diverse sedimentary rocks. In contrast to other common mixing models, this relation is appropriate to convert thermal‐diffusivity data obtained on air‐saturated samples into such reflecting water‐saturated conditions. This is of particular importance for handling data acquired from methods limited to the measurement of dry samples, for example, laser‐flash analysis. In conclusion, the applied relation is suited to model thermal‐diffusivity data of isotropic sedimentary rocks of different porosity and independent of the pore fluid.

The non-steady state CKD-EPI calculator.

The non-steady state CKD-EPI calculator.

The evolution of early diagenetic processes at the Mozambique margin during the last glacial-interglacial transition

The Mozambique continental margin experienced large variations in sedimentation rates, primarily due to re-routing of sediment deposition from the Zambezi River during the last glacial-Holocene transition. As changes in sediment accumulation and organic matter deposition impose a strong control on the formation of authigenic minerals in the sediment, the distribution of these minerals may reflect the regional paleoenvironmental and paleoclimatic evolution. Combining geochemical analyses of porewaters and sediments with a reactive transport modeling approach, we reconstruct the depositional history and its effect on pyrite formation and other biogeochemical transformations at a site on the Mozambique margin over the past 27 kyr. Fitting the model to match the observed geochemical patterns, most importantly authigenic pyrite, allowed for the reconstruction of past sulfate-methane transition zone depth, which migrated in response to changes in the sediment accumulation and organic matter deposition. Changes in sediment deposition quickly affected organoclastic sulfate reduction and associated pyrite formation, but the effect on anaerobic methane oxidation and subsequent pyrite formation occurred with a lag on the order of thousands of years. Model results reveal a transition from high diagenetic reaction rates representative of near-shore depositional environments during the late glacial maximum, to a setting typical of offshore sediments with low reaction rates at the present day. Notably, the remnants of methane and dissolved iron pools produced in the past still shape the diagenetic processes at and below the sulfate-methane transition zone today. Since deglacial shelf-flooding and corresponding changes in sediment deposition occurred along continental margins worldwide, our analysis highlights the important role of non-steady state diagenesis in continental margin sediments and its relevance for paleoceanographic interpretation of sediment cores experiencing strong variations in sediment input.

Hydrogen permeation under high pressure conditions and the destruction of exposed polyethylene-property of polymeric materials for high-pressure hydrogen devices (2)-

Aiming to elucidate physical property affecting to hydrogen gas permeability of polymer materials used for liner materials of storage tanks or hoses and sealants under high-pressure environment, as model materials with different free volume fraction, five types of polyethylene were evaluated using two methods. A convenient non-steady state measurement of thermal desorption analysis (TDA), and steady-state high-pressure hydrogen gas permeation test (HPHP) were used both under up to 90 MPa of practical pressure. The limit of TDA method of evaluation for the specimens suffering fracture during decompression process after hydrogen exposure was found. Permeability coefficient decreased with the decrease of diffusion coefficient under higher pressure condition. Specific volume and degree of crystallinity under hydrostatic environment were measured. The results showed that the shrinkage in free volume caused by hydrostatic effects of the applied hydrogen gas pressure decreases diffusion coefficient, resulting in the decrease of permeability coefficient with the pressure rise.

Dynamic thermal pleasure in outdoor environments - temporal alliesthesia

Thermal comfort research has been historically centred around the concept of “thermal neutrality”. Thermal neutrality originates from the steady-state indoor environment and is increasingly questioned when used to define the optimum sensation in outdoor environments. This calls for new criteria, designated for non-steady state and dynamically evolving outdoor settings. To address this need, we investigated thermal pleasure dynamics in outdoor environments based on thermal alliesthesia – a psychophysiological framework for understanding the hedonic responses elicited by non-steady-state thermal exposures. Detailed field studies were conducted in Sydney, Australia, during a 30-day period covering both summer and winter with a total of 35 subjects. The thermal sensation scale was quantitatively divided into four alliesthesial potential areas – two with moderate and two with strong alliesthesial potential - based on their divergence to the preferred sensation. We find that the temporal pleasure change (dP) can be predicted using thermal sensation change (dT). The results showed that linear regression performed strongly (R2 = 0.77 for summer and R2 = 0.79 for winter) in predicting dP when subjects' preceding sensation was in the strong alliesthesial potential zones – namely the ‘Hot’ and ‘Cold’ areas. When subjects' prior thermal sensation fell in the thermoneutral zone with moderate alliesthesial potential, a quadratic fit against dT provides a more reasonable prediction of dP (R2 = 0.61 for summer and R2 = 0.56 for winter). The dynamic thermal pleasure models provide a more nuanced subjective interpretation of outdoor urban spaces that includes thermal pleasure and delight. This study contributes further empirical support to the thermal alliesthesia framework and extends its application scope into outdoor thermal comfort research.

Denoising non-steady state dynamic PET data using a feed-forward neural network

The quality of reconstructed dynamic PET images, as well as the statistical reliability of the estimated pharmacokinetic parameters is often compromised by high levels of statistical noise, particularly at the voxel level. Many denoising strategies have been proposed, both in the temporal and spatial domain, which substantially improve the signal to noise ratio of the reconstructed dynamic images. However, although most filtering approaches are fairly successful in reducing the spatio-temporal inter-voxel variability, they may also average out or completely eradicate the critically important temporal signature of a transient neurotransmitter activation response that may be present in a non-steady state dynamic PET study. In this work, we explore an approach towards temporal denoising of non-steady state dynamic PET images using an artificial neural network, which was trained to identify the temporal profile of a time-activity curve, while preserving any potential activation response. We evaluated the performance of a feed-forward perceptron neural network to improve the signal to noise ratio of dynamic [11C]raclopride activation studies and compared it with the widely used highly constrained back projection (HYPR) filter. Results on both simulated Geant4 Application for Tomographic Emission data of a realistic rat brain phantom and experimental animal data of a freely moving animal study showed that the proposed neural network can efficiently improve the noise characteristics of dynamic data in the temporal domain, while it can lead to a more reliable estimation of voxel-wise activation response in target region. In addition, improvements in signal-to-noise ratio achieved by denoising the dynamic data using the proposed neural network led to improved accuracy and precision of the estimated model parameters of the lp-ntPET model, compared to the HYPR filter. The performance of the proposed denoising approach strongly depends on the amount of noise in the dynamic PET data, with higher noise leading to substantially higher variability in the estimated parameters of the activation response. Overall, the feed-forward network led to a similar performance as the HYPR filter in terms of spatial denoising, but led to notable improvements in terms of temporal denoising, which in turn improved the estimation activation parameters.

Using heat as a tracer to map and quantify water infiltration and exfiltration along a complex high energy beach face

The flux of water, nutrients, carbon and salt through the subsurface at the land-sea interface is an important control on coastal nutrient processes, salinization of coastal aquifers and carbon balances of the coastal zone. However, these fluxes are often spatially and temporally complex and difficult to quantify, especially in high-energy mesotidal systems. Here we use vertical temperature profiles along a morphologically complex mesotidal high-energy beachface to map and quantify water infiltration and exfiltration on the island of Spiekeroog, Germany. Water fluxes were quantified using heat transport calculations from three solutions to the 1D heat transport equation, and include 1) a steady state analytical solution, 2) a non-steady state numerical model and 3) a non-steady state analytical solution. The temperature profiles could clearly map areas of upwelling warm (up to 10 °C) groundwater during the winters of 2018 and 2019. These upwelling zones were focused on an intertidal runnel system and at the low water line, consistent with the current understanding of the site based on visual observations and hydrogeological models. The steady state model provided good fits to the measured data in the winter when the seawater temperatures were not changing significantly, but was less able to reproduce the measured profiles in spring when seawater was warming. The steady state flux rates ranged from −110 to −43 mm d−1 in the runnel and low water line to +43 mm d−1 towards the high water line. The dynamic numerical model successfully captured the propagation of the seawater temperature signal into the subsurface and was able to reproduce the temperature profiles during both seasons. The flux estimates tended to be larger with the numerical model, with up to −150 mm d−1 in the runnel and +110 mm d−1 towards the high water line. The non-steady state analytical solution could only be applied to a limited time series due to the difficulty of logging temperatures in the subsurface at this highly dynamic site. Up to 1.5 days of data suggested fluxes that were considerably higher than the other two methods with best-estimates of −400 to −900 mm d−1. Thermal Peclet numbers ranged from 0.2 to 2 suggesting that both conduction and advection of heat is important. This study demonstrates that the morphology of the beach face is an important control on spatial distribution of down-welling and upwelling zones along the beach and that temperature measurement combined with heat modelling are potentially useful methods for understanding the interactions between groundwater and the sea.